U.S. patent application number 17/226520 was filed with the patent office on 2021-11-04 for polyol compositions for hot melt adhesives.
The applicant listed for this patent is IFS Industries Inc.. Invention is credited to Zhijin CHEN.
Application Number | 20210340417 17/226520 |
Document ID | / |
Family ID | 1000005712760 |
Filed Date | 2021-11-04 |
United States Patent
Application |
20210340417 |
Kind Code |
A1 |
CHEN; Zhijin |
November 4, 2021 |
POLYOL COMPOSITIONS FOR HOT MELT ADHESIVES
Abstract
Disclosed are polyether and polyesters polyol condensations. The
polyols are uniquely suited for ease of manufacture and improved
adhesive characteristics particularly for low surface energy
materials. The materials can be used in urethane adhesives.
Inventors: |
CHEN; Zhijin; (Garland,
TX) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
IFS Industries Inc. |
Reading |
PA |
US |
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|
Family ID: |
1000005712760 |
Appl. No.: |
17/226520 |
Filed: |
April 9, 2021 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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15888909 |
Feb 5, 2018 |
10975277 |
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17226520 |
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14627745 |
Feb 20, 2015 |
9884981 |
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15888909 |
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61942786 |
Feb 21, 2014 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G 63/914 20130101;
C09J 175/08 20130101 |
International
Class: |
C09J 175/08 20060101
C09J175/08; C08G 63/91 20060101 C08G063/91 |
Claims
1. A method for the synthesis of a capped polymeric polyol, the
method comprising the steps of: (a) combining a polymeric polyol,
having a molecular weight greater than 500, the polyol comprising a
starter compound and repeating units of an alkylene oxide, with a
glycidyl ether or ester compound at a ratio of one glycidyl
compound per each active hydroxyl group in the polymeric polyol, to
form a mixture; and (b) reacting the mixture to form the capped
material.
2. A method for the synthesis of a capped polyester polyol, the
method comprising the steps of: (a) combining a polyol from a
carboxylic acid with a carboxyl functionality of two or more and a
hydroxyl compound with a hydroxyl functionality of two or more to
form a polyester polyol having a molecular weight of at least 500
with a glycidyl ether or ester compound at a ratio of one glycidyl
compound per each active hydroxyl group in the polymeric polyol, to
form a mixture, and (b) reacting the polyester polyol to form the
capped material.
3. A polyester polyol compound comprising a polyester polyol having
a molecular weight greater than 500 with at least one end cap
formed from a reaction of an active hydrogen in the polyester
polyol with a glycidyl compound.
4. A polyether polyol compound comprising a polyether polyol 1
having a molecular weight greater than 1000 with at least one end
cap formed from a reaction of an active hydrogen in the polyether
polyol with a glycidyl compound.
5. A polyether polyol compound comprising a polyether polyol 1
having a molecular weight greater than 500 with at least one end
cap formed from a reaction of an active hydrogen in the polyether
polyol with a glycidyl compound.
6. The polyol of claim 5 wherein the polyester comprises a
substantially linear aliphatic polyester.
7. The polyol of claim 6 wherein the aliphatic polyester comprises
the polymerization as esterification reaction product of a
dicarboxylic acid and a diol.
8. The polyol of claim 6 wherein the polyester comprises a
substantially linear polyester made from an aromatic dicarboxylic
acid in a diol.
9. The polyol of claim 5 wherein the glycidyl to compound comprises
a glycidyl ether or glycidyl ester.
10. The polyol of claim 9 wherein the glycidyl ester comprises a
carboxylic acid ester having 5 to 20 carbon atoms.
11. The polyol of claim 10 wherein the glycidyl ester comprises a
compound of formula: ##STR00008## wherein, R6 and R7 are typically
linear or branched hydrocarbyl or alkyl groups having from about
one to about 20 carbon atoms.
12. The polyol of claim 11 wherein the total carbon content of the
branched alkali group of the acid group of the glycidyl ester is
such from about 9 to about 15 carbon atoms.
13. A method for the synthesis of a capped polyester polyol, the
method comprising the steps of: (a) forming a polyol from a
aliphatic carboxylic acid with a carboxyl functionality of two or
more and an aliphatic hydroxyl compound with a hydroxyl
functionality of two or more to form a polyester polyol having a
molecular weight of at least 500 by reacting the acid with the
hydroxyl compound, at temperature greater than 190.degree. C., to
form a reaction mixture, until the acid number of the reaction
mixture is less than 0.5: and (b) reacting the polyester polyol
with a glycidyl ester at a temperature greater than 140.degree. C.
to form the capped material.
14. A polyurethane adhesive material comprising an isocyanate
compound and a glycidyl capped polyether polyester polyol.
15. The polyurethane adhesive material of claim 14 wherein the
isocyanate compound is MDI and the polyol is the polyol of claim
11.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is a continuation of U.S. patent
application Ser. No. 15/888,909 filed Feb. 5, 2018, which is a
divisional application of U.S. patent application Ser. No.
14/627,745 filed Feb. 20, 2015, which claims the benefit of U.S.
Provisional Patent Application Ser. No. 61/942,786, filed Feb. 21,
2014, which application is hereby incorporated by reference in its
entirety.
FIELD OF THE INVENTION
[0002] The compositions relate to polyol materials. The polyols are
polymeric acid or hydroxyl terminated materials that are end
capped. The polymer polyols can be used with a reactive curing
agent such as an isocyanate compounds or used in formulated curable
adhesives.
BACKGROUND OF THE INVENTION
[0003] In the preparation of polyether and polyester polyol
materials, and particularly in the manufacture of polyester
materials, control of acid number, hydroxyl number, reaction
conditions and molecular weight can be important in order to
increase polyol productivity. Improved polyol materials can also
produce improved adhesive properties in the formulated curable
adhesive materials, including urethane adhesives.
[0004] While a number of polyether and polyester polyols have been
formulated, a substantial need still exists in obtaining improved
polyether and polyester polyol preparation or processing that can
improve manufacturing efficiency, control of acid number or
hydroxyl number and molecular weight. A further need exists to
obtain improved adhesive properties in a final adhesive
formulation.
BRIEF DISCLOSURE
[0005] We have found that the use of a glycidyl ether or ester
compound as a capping agent can improve the manufacture of and the
properties of polymer polyol compounds. Capped polyol compositions
of the disclosure are substantially linear polyether or polyester
polyols with an acid number equal to or less than about 2 or a
hydroxyl number equal to or greater than 10 shows improved
properties when used in curable (i.e.) polyurethane adhesive
materials. The capped polyols when used with suitable isocyanate
reactive compounds produce improved adhesive strength in bonding
particularly low surface energy materials such as polyolefins and
ABS resins.
[0006] The processes for manufacturing the polyol compositions and
specifically polyester polyol materials are improved in terms of
efficiency and yield.
[0007] Polyether polyols are typically made by polymerizing
alkylene oxide materials to form substantially linear polymers.
[0008] Polyester polyols can be made by polymerizing
multifunctional aliphatic or aromatic carboxylic acids (two or more
carboxylic groups) with a multifunctional aliphatic or aromatic
alcohol (two or more hydroxyl groups) compounds resulting in
polyester materials having residual acidic or hydroxyl
functionality, measured by acid number or hydroxyl number. Lower
alcohol esters of the carboxylic acids can be used in the
poly-esterification.
[0009] We have found that useful precursor polyester polyol
materials having an acid number or hydroxyl number of about 5 to 30
can be reacted with a glycidyl compound. The amount of glycidyl
compound is used that reacts with residual active hydrogen (acid or
hydroxyl) to cap the polymer and complete the reaction but leaving
sufficient hydroxyl to be useful in a reaction with isocyanate. The
use of the glycidyl compound can also provide the manufacture of
the polyol material with molecular weight control and improved
adhesive properties. In the polyester, the mole ratio of
hydroxyl:carboxyl (--OH:--CO.sub.2H) can be 1.2:1 to 0.8:1 or 1.1:1
to 0.9:1. The molecular weight (M.sub.n) of the capped material is
greater than 500 and is often 1000 to 16000 or 2000 to 4000.
[0010] We have further found in manufacture of polyester polyols
particularly from dicarboxylic acids and di-hydroxyl compounds that
the glycidyl ester compound can be used to substantially reduce
manufacturing time, control molecular weight and improve the
properties of the resulting adhesive materials. The use of the
glycidyl capping agent results in reduced reaction time and
increased productivity. The glycidyl compound permits the reaction
to end before all consuming the maximum amount of the reactants. As
the concentration of the reactants is reduced by the
esterification, the reaction rate slows. At this point, if the
molecular weight is sufficient, the glycidyl agent can be used to
react with remaining active hydrogen compound to compete the
synthesis. Molecular weights are measured as number average
(M.sub.n). In this way the reaction does not need to be driven to
completion. Amounts of materials are selected such that the
hydroxyl or acid number of the finished materials is sufficient to
react with (e.g.) an isocyanate compound in a formulated
adhesive.
BRIEF DESCRIPTION OF DRAWINGS
[0011] Certain viscosity and reaction characteristics of the
claimed adhesives are shown in FIGS. 1 and 2, respectively.
[0012] FIG. 1 is a graph showing a relationship between viscosity
and average molecular weight for a precursor (linear) polyester and
a capped polyester.
[0013] FIG. 2 is a graph showing temperature versus reaction time
and temperature versus weight of water collected from the reactor
for several reaction conditions of Polyester 17.
DETAILED DISCUSSION
[0014] In a first aspect of the invention is a generic polymeric
polyol precursor compound having an acid number or a hydroxyl
number of about 5 to 30 that can be reacted with a glycidyl
compound resulting in end cap of the polyol.
[0015] In another aspect of the invention, a polyether polyol can
be manufactured by reacting a poly alkylene oxide polyol with the
glycidyl compound.
[0016] In a further aspect of the invention, a polyester polyol can
be reacted with the glycidyl compound of the invention.
Substantially linear polyester polyols of dicarboxylic acids and di
hydroxyl compound can be made with useful molecular weight and
reactivity.
[0017] In a still further aspect of the invention, the capping
agent can be used in a method for the manufacturer of a polyester
polyol using substantially linear polyester polyols of dicarboxylic
acids and di hydroxyl compound such as an aliphatic dicarboxylic
acid, and aliphatic dihydroxy compound in order to form a
preliminary polyester reaction product. When that reaction product
achieves molecular weight of at least 500 or at least 2000, an acid
number of 5 to 100 or, the precursor reaction product can be
reacted with the glycidyl compound such as a glycidyl ester
compound to complete the reaction and form the finished capped
polymeric polyol material. In this way the reaction does not have
to be forced to completion as the concentration of the acid and
hydroxyl reactants are reduced. The amount of glycidyl compound is
selected to react with acid and hydroxyl functionality leaving a
finished material with an acid number (less than or equal to 2 or
less than 1) or hydroxyl number (less than 6 or less than 12 or
less than 112) and a residual glycidyl content of less than 0.1%,
0.05 or 0.02% for further use such as in a urethane adhesive. Since
the use of the glycidyl ester compound then reacts with available
acid and hydroxyl material in the reaction product, then the polyol
synthesis is rapidly brought to completion much sooner than if left
to simply finish by the esterification polymerization.
[0018] The invention is also directed to capped polymeric polyester
polyol comprising the reaction product of a polyester polyol having
a molecular weight greater than about 500. The hydroxyl number can
be consistent with the levels disclosed herein. The glycidyl
compound can have a formula:
##STR00001##
wherein A is an ester or ether residue or moiety and O is oxygen
and wherein A can be linear or branched, saturated or unsaturated,
acyl, aliphatic or aromatic hydrocarbon radical having from 2 to 30
carbon atoms, wherein the polyol is reacted with the glycidyl
compound at a ratio of epoxy groups to hydroxyl groups as disclosed
herein.
Glycidyl Compounds
[0019] Glycidyl compound are shown in the structural formula I
as:
##STR00002##
wherein A is an ester or ether residue or moiety and O is oxygen. A
can be linear or branched, saturated or unsaturated, acyl,
aliphatic or aromatic hydrocarbon radical having from 2 to 30
carbon atoms. Alternately, glycidyl compounds, which contain
glycidyl groups bonded directly to nitrogen or sulfur (where O=S or
N) atoms can be employed in the process. Alkyl glycidyl ethers or
esters or mixtures of alkyl glycidyl ethers or esters containing
the requisite C.sub.2-30 or C.sub.4-22 alkyl substituents may be
utilized for the preparation of the capped materials.
Glycidyl Ethers
[0020] Examples of alkyl glycidyl ethers include ethyl, butyl
glycidyl ether, iso-butyl glycidyl ether, pentyl glycidyl ether,
amyl glycidyl ether, hexyl glycidyl ether, ethyl hexyl glycidyl
ether, iso-octyl glycidyl ether, n-decyl glycidyl ether, lauryl
glycidyl ether, myristyl glycidyl ether, cetyl glycidyl ether,
phenyl glycidyl ether benzyl etc.
Glycidyl Esters
[0021] Glycidyl esters are of the general structure set forth in
structural formula I are the reaction product of one or a mixture
of saturated monocarboxylic acids, preferably the alkali or
tertiary ammonium salts thereof, and a halo-substituted
monoepoxide.
[0022] Suitable saturated monocarboxylic acids which may be used to
prepare the glycidyl esters are primary secondary and tertiary
alkyl acids wherein containing 2-20 carbon atoms, more preferably
2-12 carbon atoms. Suitable such acids include neodecanoic,
neotridecanoic, and pivalic acids. A particularly preferred acid is
a neodecanoic acid prepared by the reaction of mono olefins
averaging 8-10 carbon atoms in the molecule with carbon monoxide
and water.
[0023] Suitable halo-substituted mono-epoxides which may be used to
prepare the glycidyl esters include epichlorohydrin,
1-chloro-2,3-epoxyhexane, 1-chloro-2, 3-epoxy-4-butyloctane,
1-chloro-2,3-epoxy heptane, 3-chloro-4,5-epoxydodecane,
3-chloro-4,5 epoxy nonane, 1-chloro-2,3-epoxy-4-cyclohexyloctane
and like materials.
[0024] Glycidyl esters of this type and their method of synthesis
are well known in the art and are particularly described in the
aforementioned. U.S. Pat. Nos. 3,178,454 and 3,075,999.
[0025] Useful glycidyl esters are shown in U.S. Pat. No. 6,433,217
and are represented by the following formula II:
##STR00003##
In the formula, R6 and R7 are typically linear or branched
hydrocarbyl or alkyl groups having from about one to about 20
carbon atoms. Wherein the total carbon content of the branched
alkali group of the acid group of the glycidyl ester as from about
5 to 25 carbon atoms and for certain embodiments from about 9 to
about 15 carbon atoms. The glycidyl ester compositions useful in
the compositions and processes disclosed herein are exemplified in
the publication of Momentum entitled Cardura E10P.
Polyol for Capping Reaction
[0026] Polyols can be polyether polyols, which are made by the
reaction of alkylene oxides or epoxides with active hydrogen
containing starter compounds, or polyester polyols, which are made
by the polycondensation of multifunctional carboxylic acids and
multifunctional hydroxyl compounds.
Polyester Polyols
[0027] One useful class of polyester polyols are manufactured by
the direct poly-esterification of high-purity diacids (or lower
alcohol esters) and glycols, such as adipic acid and 1,4-butanediol
at elevated temperature until the desired molecular weight (about
500 to 8000) is achieved. Polyester polyols are usually more
expensive and more viscous than polyether polyols, but they make
polyurethanes with better solvent, abrasion, and cut resistance.
Other polyester polyols are based on trans-esterification
(glycolysis) of poly(ethylene terephthalate) (PET) or dimethyl
terephthalate (DMT) with glycols such as diethylene glycol.
[0028] Polyester polyol can be made from the following hydroxyl
diols and triols reacted with dicarboxylic acid materials.
TABLE-US-00001 Diols and triols used for polyester polyol synthesis
Hydroxyl number, mg No. Polyol MW, daltons KOH/g Diols 1 Ethylene
glycol (EG) 62.07 1807.6 2 Diethylene glycol (DEG) 106.12 1057.2 3
1,2 Propylene glycol 76.10 1474.3 (PG) 4 1,4 Butanediol (BD) 90.12
1245.0 5 Neopentyl glycol (NPG) 104.0 1078.8 6 1,6 Hexanediol
118.18 949.3 7 3-methyl-1,5- 118 950.8 pentanediol (MPD) 8
1,9-Nonanediol (ND) 160 710.3 Triols 1 Glycerol 92.10 1827.3 2
Tri-methylol propane 122 1379.5 (TMP)
TABLE-US-00002 Acid number, No. Dicarboxylic acid MW, Daltons mg
KOH/g Aliphatic dicarboxylic acids used for polyester polyol
synthesis 1 Adipic acid (AA) 146.14 767.78 2 Glutaric acid 132.12
849.2 3 Succinic acid 118.09 950.1 4 Sebacic acid 202.0 555.4 5
Azelaic acid 186.0 603.2 6 Dodecanedioic acid 230.3 487.2 Aromatic
dicarboxylic acids and derivatives used for polyester polyol
synthesis 1 Iso-phthalic acid (IPA) 166.13 675.3 2 Phthalic
anhydride 148.12 757.4 3 Terephthalic acid 166.13 675.3
Polyether Polyol
[0029] Polyols use dipropylene glycol (functionality 2), glycerin
(functionality 3) or a sorbitol/water solution (functionality
2.75). sucrose (functionality 8), sorbitol(functionality 6),
toluene diamine (equivalent of 4 hydroxyl). Propylene oxide and/or
ethylene oxide is added to the initiators until the desired
molecular weight (greater than about 500 or 8000) is achieved. The
order of addition and the amounts of each oxide affect many polyol
properties, such as compatibility, water-solubility, and
reactivity. Polyols made with only propylene oxide are terminated
with secondary hydroxyl groups and are less reactive than polyols
capped with ethylene oxide, which contain a higher percentage of
primary hydroxyl groups.
[0030] Polyether polyols can be represented by:
##STR00004##
Wherein R.sub.1 represents an initiator compound residue, R.sub.2
is a C.sub.2-4 alkylene group and n is a number of 2 to 100. The
group R.sub.2--O-- also represents a polymer residue of polymerized
ethylene oxide, propylene oxide or mixtures thereof. Due to their
high hydroxyl number dendritic polyols are not useful in the
claimed compositions.
TABLE-US-00003 Initiators used for the synthesis of polyols
Molecular weight Hydroxyl number Starter Functionality (Daltons)
(mg KOH/g) Water 2 18 6233.3 Ethylene glycol 2 62 1807.9 Diethylene
2 106 1057.4 glycol 1,2 Propylene 2 76.1 1474.6 glycol Dipropylene
2 134.2 836.3 glycol (DPG) Glycerin 3 92 1829 Tri-methylol 3 134.2
1254.1 propane 1,2,6 3 134 1255 Hexanetriol Triethanolamine 3 146
1152.7 Ethylenediamine 4 60 3740 Pentaerythritol 4 136.15
1648.18
Polymer Polyol Capping Reaction
[0031] The capping reaction combines a glycidyl compound with the
polymer polyol and reacts the glycidyl compound with a group with
an active hydrogen such as a carboxylic acid (--CO.sub.2H) or
hydroxyl (--OH) group. A resulting capped polyether structures can
be represented as IVa or IVb:
##STR00005##
[0032] Capped polyester is represented by Va or Vb:
##STR00006##
[0033] wherein R.sub.8O-- represents the residue of --OH
functionality of a polyether polyol or --OH functionality of a
polyester polyol as structure VI:
##STR00007##
represents a residue of the acid functionality of a polyester
polyol. The glycidyl reaction creates secondary hydroxyls or
primary hydroxyls depending on the presence of catalyst that can
react in a urethane adhesive. Amounts of materials are selected
such that the hydroxyl or carboxylic acid functionality is fully
reacted and made derivative by a matching amount of glycidyl
compound. At the end of the reaction little or no free carboxylic
acid, epoxy or glycidyl functionality should be detected.
Adhesive Technology
[0034] The remaining active hydrogen groups, primarily hydroxyl
groups, in the capped polyols can be used to formulate curing
adhesives. Any curing agent that can react with the active hydrogen
or hydroxyl can be used in an adhesive. Useful adhesives are
urethane and epoxy materials.
[0035] Polyurethanes are produced by reacting an isocyanate
containing two or more isocyanate groups with a polyol containing
on average two or more hydroxyl groups per molecule typically in
the presence of a catalyst.
[0036] Isocyanates are very reactive materials. Aromatic
isocyanates, diphenylmethane diisocyanate (MDI) or toluene
diisocyanate (TDI) are more reactive than aliphatic isocyanates,
such as hexamethylene diisocyanate (HDI) or isophorone diisocyanate
(IPDI). Isocyanates are difunctional; two isocyanate groups per
molecule. An important exception to this is polymeric diphenyl
methane diisocyanate, which is a mixture of molecules with two-,
three-, and four- or more isocyanate groups. In cases like this the
material has an average functionality greater than two, commonly
2.7.
[0037] A. The capped polyols of the disclosure that are used to
make polyurethane adhesives are not "pure" compounds since they are
often mixtures of similar molecules with different molecular
weights and mixtures of molecules that contain different numbers of
hydroxyl groups, which is why the "average functionality" is often
mentioned The polymerization reaction makes a polymer containing
the urethane linkage, --RNHCOOR'-- and is catalyzed by tertiary
amines, such as 1,4-diazabicyclo [2.2.2] octane (also called DABCO
or TEDA), DMDEE (2,2'-dimorpholino diethyl ether) and metallic
compounds, such as dibutyltin dilaurate or bismuth octanoate.
[0038] Aliphatic and cycloaliphatic isocyanates are used in smaller
volumes, most often in coatings and other applications where color
and transparency are important. The most important aliphatic and
cycloaliphatic isocyanates are 1,6-hexamethylene diisocyanate
(HDI), 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane
(isophorone diisocyanate, IPDI), and 4,4'-diisocyanato dicyclohexyl
methane, (H.sub.12MDI or hydrogenated MDI).
[0039] Chain extenders are low molecular weight hydroxyl and amine
terminated compounds that play an important role in the polymer
morphology. The choice of chain extender also determines flexural,
heat, and chemical resistance properties. The most important chain
extenders are ethylene glycol, 1,4-butanediol (1,4-BDO or BDO),
1,6-hexanediol, cyclohexane dimethanol and hydroquinone
bis(2-hydroxyethyl) ether (HQEE).
[0040] Polyurethane catalysts can be classified into two broad
categories, amine compounds and metal complexes. Traditional amine
catalysts have been tertiary amines such as triethylene diamine
(TEDA, 1,4-diazabicyclo[2.2.2]octane or DABCO), dimethyl
cyclohexylamine (DMCHA), and dimethyl ethanolamine (DMEA). Tertiary
amine catalysts are selected based on whether they drive the
urethane (polyol+isocyanate, or gel) reaction or the isocyanate
trimerization reaction (e.g., using potassium acetate, to form
isocyanurate ring structure). Catalysts that contain a hydroxyl
group or secondary amine, which react into the polymer matrix, can
replace traditional catalysts thereby reducing the amount of amine
that can come out of the polymer.
[0041] Suitable additives for use in the present invention may be
any compound which will not interfere with the efficacy of the
other components in the adhesive composition and which increases
adhesion. Suitable additives include, but are not limited to,
reactive or non-reactive polymers, fillers, plasticizers, viscosity
control agents, defoamers and stabilizers.
Exemplary Section
[0042] The following examples and data (reflected in the figures of
the conversion of the materials into polyester) show the utility of
the processes of the invention in obtaining high quality polyol
materials for use in the compositions of the disclosure. The
preparations are exemplary of the aspect of the invention using
polyester polyol materials but should not be used in unduly
limiting the scope of the claims.
[0043] In the following polymerization reactions followed by the
capping reaction, the reactants are combined in a conventional oil
jacketed heated polyester reactor vessel equipped with a nitrogen
bubbler that acts to remove volatile materials such a reaction
byproduct water, reduce color formation and agitate the
mixture.
[0044] In the formation of the capped polyester polyol, the
dicarboxylic acid and the dihydroxyl compound is added to the
vessel and heated to 140.degree. C. Water a byproduct of
esterification is formed and removed by nitrogen. After water
generation slows, the temperature is gradually increased to
220.degree. C. and the reaction is continued until the acid number
falls to less than 20 preferable less than 10. At this point the
molecular weight is greater than about 3000.
[0045] The reaction mixture is cooled and the glycidyl ester is
then added to react with remaining acid groups. The reaction is
heated to 140-190.degree. C. This reaction forms secondary or
primary hydroxyl groups with glycidyl ring opening.
Examples 1-6
[0046] Materials--Adipic acid, CAS number 124-04-9, F.W. 146.14,
melting point 150.85.degree. C., boiling point 337.5.degree. C.,
flash point 196.degree. C.; 1,6-hexanediol, CAS number 6920-22-5,
F.W. 118.18, melting point 40-42.degree. C., boiling point
253-260.degree. C., flash point 135.degree. C. (Tag Closed Cup);
Glycidyl ester Cardura E10P, boiling range 251-278.degree. C.
(5-95%), epoxide equivalent 240 g/mol, viscosity 7 mPa/s
(23.degree. C.), high flash point.
Synthesis of Polyester Precursor
TABLE-US-00004 [0047] Molar ratio between hydroxyl and Adipic Acid
1,6-Hexanediol carboxyl EX. 1-6 (g) (g) groups Polyester 900 753
1.035:1 9, 11, 15, (54.44 wt %) (45.56 wt %) 16L, 16R Polyester 13
900 705 0.969:1 (56.07 wt %) (43.93 wt %)
[0048] 753 g of 1,6-hexanediol (for polyester 9, 11, 15, 16L and
16R) and 900 g of adipic acid were reacted under a nitrogen
atmosphere at a temperature in the range from 140 to 200.degree. C.
After water which had been formed in the reaction had been removed
by distillation, the temperature was increased to range from
200-230.degree. C. After the acid number had fallen to the expected
data, the reaction was stopped. Then we measured the acid number
and viscosity.
TABLE-US-00005 Brookfield Viscosity Acid Number Mn(calculated (cP,
80.degree. C., EX. 1-6 (mg KOH/g) from theory) spindle #31, 20 rpm)
Polyester 9 8.22 (12 h) 3389 2432 Polyester 11 9.10 (13 h) 3219
2064 Polyester 15 11.70 (12 h) 2802 1360 Polyester 16L 10.16 (14 h)
3035 N/A Polyester 16R 10.56 (14 h) 2971 N/A Polyester 13 27.24 (9
h) 2881 1600
Capping Reaction
[0049] W E .times. 1 .times. 0 .times. P = W p .times. o .times. l
.times. y .times. e .times. ster * AN 5 .times. 6 .times. 1 .times.
1 .times. 0 * 240 .times. .times. ( g ) ##EQU00001##
Reaction Proportions
TABLE-US-00006 [0050] Acid Number OH number of polyester of
polyester W.sub.polyester W.sub.E10P EX. 1-6 (mg KOH/g) (mg KOH/g)
(g) (g) Polyester 9 8.22 24.89 1221 42.93 (3.37%) Polyester 11 9.10
25.77 1272 49.51 (3.75%) Polyester 15 11.70 28.35 1336 66.86
(4.77%) Polyester 16L 10.16 26.82 1436 62.40 (4.16%) Polyester 16R
10.56 27.22 1436 64.86 (4.32%) Polyester 13 27.24 11.72 1289 150.19
(10.44%)
[0051] Polyester precursor was heated to 160.degree. C. in nitrogen
atmosphere, and then Cardura E10P was added into the reactor in 30
minutes in droplets. The reaction temperature was increased to
190.degree. C. in 3 hours and hold for 3 hours.
TABLE-US-00007 Brookfield OH number Mn Viscosity Acid Number of
polyester (calculated (cP, 80.degree. C., EX. 2-6 (mg KOH/g) (mg
KOH/g) from theory) spindle #31, 20 rpm) Polyester 11 0.93 (8.76)
32.63 (24.80) 3344 (3219) 2256 Polyester 15 1.22 (11.14) 36.92
(27.00) 2942 (2802) 1472 Polyester 16L 0.86 (9.73) 34.57 (25.70)
3167 (3035) 1856 Polyester 16R 1.11 (10.10) 35.03 (26.04) 3105
(2971) 1696 Polyester 13 2.00 (24.40) 32.90 (10.50) 3215 (2881)
1632
[0052] The reaction time of polyester precursor can be shortened
from greater than 20 hours to 15 hours or less. The reaction
temperature of polyester precursor ranges from 140 to 230.degree.
C. and holding at 220-230.degree. C. for not less than 9 hours. The
reaction of acid carboxyl with epoxy is stoichiometric. Final
reaction temperature ranges from 160-190.degree. C. The residual
epoxy in the final products is less than 0.02 mmol/g (epoxy residue
is 0.032%). FIG. 1 shows the viscosity of the precursor polyester
and the capped polyester.
Example 7
[0053] Materials--Adipic acid, CAS number 124-04-9, F.W. 146.14,
melting point 150.85.degree. C., boiling point 337.5.degree. C.,
flash point 196.degree. C.; 1,6-hexanediol, CAS number 6920-22-5,
F.W. 118.18, melting point 40-42.degree. C., boiling point
253-260.degree. C., flash point 135.degree. C. (Tag Closed Cup);
Cardura E10P, boiling range 251-278.degree. C. (5-95%), epoxide
equivalent 240 g/mol, viscosity 7 mPa/s (23.degree. C.), high flash
point.
Synthesis of Polyester Precursor
TABLE-US-00008 [0054] Molar ratio between hydroxyl and Adipic Acid
1,6-Hexanediol carboxyl EX. 7 (g) (g) groups Polyester 17 12910
10800 1.0345:1 (54.45 wt %) (45.55 wt %)
Reaction Procedure
[0055] 10800 g of 1,6-hexanediol and 12910 g of adipic acid were
reacted under a nitrogen atmosphere at a temperature in the range
from 140 to 200.degree. C. (in 5 hours). After most of the water
which had been formed in the reaction had been removed by
distillation, the temperature was increased to range from
220-230.degree. C. (in 2 hours) and hold for 8.5 hours. After the
acid number had fallen to the expected data, the reaction was
stopped. Measure the acid number.
Results
TABLE-US-00009 [0056] Mn Acid Number (calculated EX. 7 (mgKOH/g)
from theory) Polyester 17 7.95 (15.5 h) 3452
Synthesis Determination of the Dosage of Cardura E10P
[0057] W E .times. 1 .times. 0 .times. P = W p .times. o .times. l
.times. y .times. e .times. ster * AN 5 .times. 6 .times. 1 .times.
1 .times. 0 * 240 .times. .times. ( g ) ##EQU00002##
Recipes
TABLE-US-00010 [0058] Acid Number OH number of polyester of
polyester W.sub.polyester W.sub.E10P EX. 7 (mgKOH/g) (mgKOH/g) (g)
(g) Polyester 17 7.95 24.56 20581 697.4 (3.28%)
Reaction Procedure
[0059] Polyester precursor was cooled to 140.degree. C. in nitrogen
atmosphere, then Cardura E10P was added into the reactor in 20
minutes. The reaction temperature was increased to 180.degree. C.
in 2 hours and hold for 2 hours. Stop the reaction when the acid
number below 1 mgKOH/g.
Results
TABLE-US-00011 [0060] Brookfield OH number Mn Viscosity Acid Number
of polyester (calculated (cP, 80.degree. C., EX. 7 (mgKOH/g)
(mgKOH/g) from theory) spindle #31, 20 rpm) Polyester 17 0.45 31.03
3565 3536
Reaction Condition of Polyester 17 (See FIG. 2 for Graphical
Representation)
TABLE-US-00012 [0061] Reaction Outside Inside Condensor H2O time
(hr) T .degree. C.) T (.degree. C.) T(.degree. C.) wt. (g) -0.75
160.0 112 24 0 -0.5 160.0 122 25 0 -0.2 160.0 139 30 0 -0.08 165.6
137.7 74 0 0 165.6 136.8 95.3 0 0.5 168.3 139.5 98.5 350 1 173.9
140.4 96.2 815 1.5 179.4 148.1 92.6 1275 2 189.4 154.5 91.7 1575
2.5 199.4 167.5 91.7 1865 3 205.0 177.7 90.2 2090 3.5 210.6 186.2
85.8 2310 4 215.6 192.1 82.6 2410 4.5 221.1 197.1 77.3 2480 5 226.7
200.5 74 2530 5.5 232.2 206.1 71.5 2580 6 237.8 212.2 67.4 2615 7
237.8 221 63.1 2660 10 243.3 224.7 46 2780 12 243.3 224.4 38.8 2812
13 243.3 224.7 36.4 2825 15 243.3 223.6 34.1 2842 15.5 243.3 224 33
2846
CONCLUSION
[0062] The reaction time of polyester precursor can be shortened
into 16 hours.
[0063] Reaction temperature of polyester precursor is range from
140 to 230.degree. C. and holding at 220-230.degree. C. for 8-9
hours.
[0064] The reaction of carboxyl with epoxy is in stoichiometry.
Reaction temperature ranges from 140-180.degree. C. Reaction time
is around 5 hours.
[0065] The residual epoxy group in the final products is less than
0.02 mmol/g (epoxy residue is 0.032%).
Adhesive
Examples
TABLE-US-00013 [0066] g eq. wt. % wt OH NCO 800 Adhesive Example 1
1 Poly propylene 15.750 1000 15.7500% 0.0158 x 126.00 glycol
PPG2000 2 Capped 22.000 1750 22.0000% 0.0126 x 176.00 Polyester 11
3 Linear saturated 17.500 2550 17.5000% 0.0069 x 140.00 Dynacol
7250 polyester polyol EG/Hexane diol neopentyl glycol adipic acid
ester 4 CAPA5600 Capro- 10.000 25000 10.0000% 0.0004 x 80.00
lactone polyester 5 3500 HAT Hexane 22.000 1750 22.0000% 0.0126 x
176.00 diol adipic acid terephthalic acid ester 6 BYK070 defoamer
0.100 10000000 0.1000% 0.0000 x 0.80 7 MDI 12.600 125 12.6000% x
0.1008 100.80 8 B. DMDEE 0.050 10000000 0.0500% x x 0.40 C.
(2,2'-dimorpholino diethylether 100.00% 800.00 100.0000 NCO % 2.21%
0.0482 0.1008 Adhesive Example 2 1 PPG2000 15.750 1000 15.7500%
0.0158 x 126.00 2 Capped 22.000 1750 22.0000% 0.0126 x 176.00
polyester 13 3 Dynacol7250 17.500 2550 17.5000% 0.0069 x 140.00 4
CAPA5600 10.000 25000 10.0000% 0.0004 x 80.00 5 3500HAT 22.000 1750
22.0000% 0.0126 x 176.00 6 BYK070 0.100 10000000 0.1000% 0.0000 x
0.80 7 MDI 12.600 125 12.6000% x 0.1008 100.80 8 DMDEE 0.050
10000000 0.0500% x x 0.40 100.00% 800.00 100.0000 NCO % 2.21%
0.0482 0.1008 Comparative Adhesive Example 1 PPG2000 15.750 1000
15.7500% 0.0158 x 126.00 2 3500 molecular 22.000 1750 22.0000%
0.0126 x 176.00 weight hexane- adipic acid polyester polyol 3
Dynacol7250 17.500 2550 17.5000% 0.0069 x 140.00 4 CAPA5600 10.000
25000 10.0000% 0.0004 x 80.00 5 3500HAT 22.000 1750 22.0000% 0.0126
x 176.00 6 BYK070 0.100 10000000 0.1000% 0.0000 x 0.80 7 MDI 12.600
125 12.6000% x 0.1008 100.80 8 DMDEE 0.050 10000000 0.0500% x x
0.40 100.00% 800.00 100.0000 NCO % 2.21% 0.0482 0.1008 Vise Open
Adhesive Ex (250.degree. F.) cP time, Sec, Bond ABS/Wood 1 18850 70
Good 2 16480 100 Good Comparative 17120 60 N/A
Comp. Ex. and Examples 1 and 2 are same percentage but Comp. Ex. is
with straight molecular weight hexane-adipic acid polyester polyol
Ex. 1 is with Polyester 11 (with 3-4% Cardura) and Ex. 2 is with
10% Cardura capped polyester polyols. In the case of 22% polyester
polyols in the formula, with low level Cardura (3-4%), the physical
property are almost the same as regular polyester polyol. With
higher Cardura, the finished viscosity is a little lower but with
longer open time, which is because the Cardura use reduces the
crystalline behavior. Lower viscosity and longer open time are
often desired in process or in application.
[0067] As can be seen in the tables of data, the processes using
the compositions disclosed above produce quality polyester polyol
materials in a shortened period of time with substantially complete
conversion to a useful polyol material with minimal residual acid
or hydroxyl minimal residual acid functionality. The hydroxyl
functionality of the polyol remains since in the reaction between
the glycidyl ether or glycidyl ester materials and the polyol a new
hydroxyl group is formed in the reaction that remains available for
reaction with the isocyanate compound in a urethane adhesive.
[0068] The claims may suitably comprise, consist of, or consist
essentially of, or be substantially free of any of the disclosed or
recited elements. The invention illustratively disclosed herein can
also be suitably practiced in the absence of any element which is
not specifically disclosed herein. The various embodiments
described above are provided by way of illustration only and should
not be construed to limit the claims attached hereto. Various
modifications and changes may be made without following the example
embodiments and applications illustrated and described herein, and
without departing from the true spirit and scope of the following
claims
* * * * *