CN108997570A - A kind of dimer acid modified copolyester hot melt adhesive and preparation method thereof - Google Patents
A kind of dimer acid modified copolyester hot melt adhesive and preparation method thereof Download PDFInfo
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- CN108997570A CN108997570A CN201810849720.3A CN201810849720A CN108997570A CN 108997570 A CN108997570 A CN 108997570A CN 201810849720 A CN201810849720 A CN 201810849720A CN 108997570 A CN108997570 A CN 108997570A
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- melt adhesive
- hot melt
- preparation
- copolyester hot
- acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
Abstract
The present invention provides a kind of preparation methods of dimer acid modified copolyester hot melt adhesive, include the following steps: that reaction kettle is added in the dimeric dibasic acid containing 36 carbon atoms, the dihydric alcohol containing 2-8 carbon atom and catalyst by (1) according to the ratio, in 160-210 DEG C of completion esterification after mixing；(2) thermoplastic polyester and stabilizer are added to the system after completing esterification in step (1), and it is warming up to 250-260 DEG C, after reaction system becomes clear, constant temperature keeps 10-60min, 60-140Pa is depressurized in 250-260 DEG C of constant temperature, polycondensation 1-4h discharges to after reaching required viscosity, and copolyester hot melt adhesive is made.The preparation method rapid reaction, high income, obtained hot melt adhesive have the characteristics such as fusing point high and low temperature tolerance is strong, melting viscosity is small, can meet the needs of many industries are to high-melting-point, low temperature resistant polyester hot-melt adhesive.
Description
Technical field
The present invention relates to copolyester hot melt adhesive technical fields, and in particular, to the present invention relates to a kind of dimer acid modified
Copolyester hot melt adhesive and preparation method thereof.
Background technique
Polyester hot-melt adhesive has the characteristics such as bonding force strong, quick solidifying, good weatherability and is widely used.But current high temperature
The polyester hot-melt adhesive of shelves is because crystallinity height, molecule chain rigidity are strong, the poor and easy embrittlement of most lower temperature resistance, and high molecular weight
Co-polyester melt viscosity is often bigger.These deficiencies make the application field of polyester hot-melt adhesive by larger limitation.
Chinese patent CN103421460A discloses the preparation side of a kind of crystallization and transparent high-melting-point copolyester hot melt adhesive
Method.Product crystallization and transparent, bonding force is strong, and dry cleaning resistance is good, and fusing point is high, have adapt to apply under the high temperature conditions it is excellent
Point.
Chinese patent CN1340585 illustrates the manufacturing method of polyester thermosol with high smelting point.The product that the method obtains has
The advantages that adaptation is applied under the high temperature conditions, crystallization rate is fast, curing time is short.
Chinese patent CN102492388A provides a kind of polyester thermosol with high smelting point with preferable mobility.The hot melt
Glue sticking is strong, there is preferable flowing guarantee property and fabulous wetting levelability in applied at elevated temperature.
The soft segments ratio very little such as methene chain, ehter bond that can be introduced with the high-melting-point copolyesters in first-class patent,
Limited on the cold tolerance of material and melting viscosity influence, performance is to be improved.
Summary of the invention
The present invention provides a kind of dimer acid modified copolyester hot melt adhesive and preparation method thereof, preparation method reaction is fast
Speed, high income, obtained hot melt adhesive have the characteristics such as fusing point high and low temperature tolerance is strong, melting viscosity is small, can meet many rows
Demand of the industry to high-melting-point, low temperature resistant polyester hot-melt adhesive.
Technical scheme is as follows: a kind of preparation method of dimer acid modified copolyester hot melt adhesive, including as follows
Step:
(1) reaction is added in the dimeric dibasic acid containing 36 carbon atoms, the dihydric alcohol containing 2-8 carbon atom and catalyst according to the ratio
Kettle, in 160-210 DEG C of completion esterification after mixing；
(2) thermoplastic polyester and stabilizer are added to the system after completing esterification in step (1), and are warming up to 250-
260 DEG C, after reaction system becomes clear, constant temperature keeps 10-60min, is depressurized to 60-140Pa in 250-260 DEG C of constant temperature,
Polycondensation 1-4h discharges to after reaching required viscosity, and copolyester hot melt adhesive is made.
Preferably, being additionally added binary of fatty acids containing 6-18 carbon atom in step (1) described reaction kettle and containing 8 carbon originals
The binary aromatic carboxylic acid of son.
Preferably, the binary of fatty acids is selected from 1,6- adipic acid, 1,8- suberic acid, 1,10- decanedioic acid, 1,12- 12
One of docosandioic acid, 1,14- tetracosandioic acid, octadecane diacid or several mixtures.
Preferably, the binary aromatic carboxylic acid is terephthalic acid (TPA) or/and M-phthalic acid.
Preferably, the dihydric alcohol is selected from ethylene glycol, 1,3-PD, 1,4-butanediol, 1,3-BDO, 2- methyl-
One of 1,3- propylene glycol, 1,5- pentanediol, neopentyl glycol, 1,6-HD, 1,4 cyclohexane dimethanol, diethylene glycol (DEG) or number
The composition of kind.
Preferably, the molar ratio of the binary of fatty acids and the dihydric alcohol is 1:2.0~2.5.
Preferably, the catalyst is selected from titanium system, tin class or antimony system, the total dosage of catalyst is the binary of fatty acids and institute
State the 0.3%-1.5% of dihydric alcohol quality summation.
Preferably, the catalyst is butyl titanate.
Preferably, the thermoplastic polyester is selected from polyethylene terephthalate (PET), poly terephthalic acid propylene glycol
One or several kinds of combinations of ester (PTT), polybutylene terephthalate (PBT) (PBT), the total dosage of thermoplastic polyester are described two
0.5-3.0 times of first fatty acid and the dihydric alcohol quality summation.
Preferably, the stabilizer is triphenyl phosphite, dosage is the binary of fatty acids and the dihydric alcohol matter
Measure the 0.1%-1% of summation.
The invention has the benefit that the preparation method of the dimer acid modified copolyester hot melt adhesive using dimeric dibasic acid into
Row chemical copolymerization modified poly ester hot melt adhesive, the preparation method rapid reaction, high income, obtained hot melt adhesive have fusing point it is high,
The characteristics such as cold tolerance is strong, melting viscosity is small, greatly improve the weatherabilities such as the cold tolerance of polyester thermosol with high smelting point
It can and process character of use.
Specific embodiment
In order to make goal of the invention of the invention, technical solution and technical effect are more clearly understood, below with reference to specific reality
Applying mode, the present invention is described further.It should be understood that specific embodiment described herein, for explaining only the invention,
It is not intended to limit the present invention.
Embodiment 1
A kind of preparation method of dimer acid modified copolyester hot melt adhesive, by 168.3g dimeric dibasic acid, 54.1g1,4- butanediol
Reaction kettle is added with 0.2133g butyl titanate, is rapidly heated to 160 DEG C, then is warming up to 210 DEG C with 60 DEG C/h rate, maintains
Reach theoretical value to water outlet, completes esterification；Then 198.1gPBT and 0.13g triphenyl phosphite is added to reaction system,
And 255 DEG C are warming up to, and after reaction system becomes clear, constant temperature keeps 10min, it is slowly decompressed to 60Pa, polycondensation 1.5h, after
220 DEG C of dischargings are cooled to, copolyester hot melt adhesive is made.It is 176 DEG C by the fusing point that hot stage melting point determination instrument measures the hot melt adhesive,
Measuring it by low temperature folding resistant test can tolerate -40 DEG C of low temperature not brittle failures, measure it in 230 DEG C of viscosity by Brookfield viscometer
For 10684cps.
Embodiment 2
A kind of preparation method of dimer acid modified copolyester hot melt adhesive, by 8.3g M-phthalic acid, 16.6g terephthaldehyde
Reaction kettle is added in acid, 84.2g dimeric dibasic acid, 54.5g1,4- butanediol and 0.5g butyl titanate, is rapidly heated to 160 DEG C, then with
60 DEG C/h rate is warming up to 210 DEG C, maintains to water outlet to reach theoretical value, completes esterification；Then 154.2gPBT () is added
With 0.11g triphenyl phosphite to reaction system, and 255 DEG C are warming up to, after reaction system becomes clear, constant temperature is kept
10min is slowly decompressed to 60Pa, polycondensation 1h, after be cooled to 220 DEG C of dischargings, be made high-melting-point copolyester hot melt adhesive.Pass through thermal station
The fusing point that melting point detector measures the hot melt adhesive is 191 DEG C, and measuring its brittle failure temperature by low temperature folding resistant test is -17 DEG C, is led to
Cross Brookfield viscometer measure its in 230 DEG C viscosity be 12245cps.
Embodiment 3
A kind of preparation method of dimer acid modified copolyester hot melt adhesive, by 8.3g M-phthalic acid, 16.6g1,6- oneself two
Reaction kettle is added in acid, 84.2g dimeric dibasic acid, 54.5g 1,3-PD, 0.2133g butyl titanate, is rapidly heated to 160 DEG C,
210 DEG C are warming up to 60 DEG C/h rate again, maintains to water outlet to reach theoretical value, completes esterification；Then it is poly- that 35.55g is added
Propylene glycol ester terephthalate and 0.711g triphenyl phosphite are warming up to 250 DEG C to reaction system, become clear to reaction system
It is clear it is bright after, constant temperature keep 20min, be slowly decompressed to 80Pa, polycondensation 2h discharges to after reaching required viscosity, after be cooled to 220
DEG C discharging, be made high-melting-point copolyester hot melt adhesive.It is 190 DEG C by the fusing point that hot stage melting point determination instrument measures the hot melt adhesive, leads to
Crossing low temperature folding resistant test and measuring its brittle failure temperature is -18 DEG C, and measuring it in 230 DEG C of viscosity by Brookfield viscometer is
12245cps。
Embodiment 4
A kind of preparation method of dimer acid modified copolyester hot melt adhesive, by 8.3g1,14- tetracosandioic acid, 16.6g pairs
Reaction kettle is added in phthalic acid, 84.2g dimeric dibasic acid, 54.5g neopentyl glycol and 0.8g butyl titanate, is rapidly heated to 160 DEG C,
210 DEG C are warming up to 60 DEG C/h rate again, maintains to water outlet to reach theoretical value, completes esterification；Then it is poly- that 154.2g is added
Ethylene glycol terephthalate and 0.11g triphenyl phosphite are warming up to 260 DEG C to reaction system, become clear to reaction system
It is clear it is bright after, constant temperature keep 60min, be slowly decompressed to 140Pa, polycondensation 4h, after be cooled to 220 DEG C of dischargings, be made high-melting-point be total to
Polyester hot-melt adhesive.It is 190 DEG C by the fusing point that hot stage melting point determination instrument measures the hot melt adhesive, it is measured by low temperature folding resistant test
Brittle failure temperature be -17.5 DEG C, by Brookfield viscometer measure its in 230 DEG C viscosity be 12250cps.
Embodiment 5
A kind of preparation method of dimer acid modified copolyester hot melt adhesive, by 8.3g octadecane diacid, 16.6g terephthaldehyde
Reaction kettle is added in acid, 84.2g dimeric dibasic acid, 54.5g diethylene glycol (DEG) and 1.1665g antimony system, is rapidly heated to 160 DEG C, then with 60 DEG C/h
Rate is warming up to 210 DEG C, maintains to water outlet to reach theoretical value, completes esterification；Then 213.3g poly terephthalic acid is added
Butanediol ester and 0.5g triphenyl phosphite are warming up to 255 DEG C to reaction system, permanent after reaction system becomes clear
Temperature keeps 10min, is slowly decompressed to 100Pa, polycondensation 3h, after be cooled to 220 DEG C of dischargings, obtained high-melting-point copolyester hot melt adhesive.
By hot stage melting point determination instrument measure the hot melt adhesive fusing point be 192 DEG C, by low temperature folding resistant test measure its brittle failure temperature be-
16 DEG C, by Brookfield viscometer measure its in 230 DEG C viscosity be 12250cps.
Embodiment 6
A kind of preparation method of dimer acid modified copolyester hot melt adhesive, by 8.3g1,8- suberic acid, 16.6g terephthaldehyde
Reaction kettle is added in acid, 84.2g dimeric dibasic acid, 54.5g, 1,4-CHDM and 1.0g tin class, is rapidly heated to 160 DEG C, then
210 DEG C are warming up to 60 DEG C/h rate, maintains to water outlet to reach theoretical value, completes esterification；Then it is poly- to benzene that 200g is added
Naphthalate and 0.0711g triphenyl phosphite are warming up to 255 DEG C to reaction system, become to reaction system and clarify
After transparent, constant temperature keeps 10min, is slowly decompressed to 60Pa, polycondensation 1h, after be cooled to 220 DEG C of dischargings, obtained high-melting-point copolyesters
Hot melt adhesive.It is 190 DEG C by the fusing point that hot stage melting point determination instrument measures the hot melt adhesive, its brittle failure is measured by low temperature folding resistant test
Temperature be -18 DEG C, by Brookfield viscometer measure its in 230 DEG C viscosity be 12230cps.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
Specific implementation of the invention is only limited to these instructions.For those of ordinary skill in the art to which the present invention belongs, exist
Under the premise of not departing from present inventive concept, architectural form cans be flexible and changeable, can be with derivative series product.It only makes several
Simple deduction or replace all shall be regarded as belonging to present invention scope of patent protection determined by the appended claims.
Claims (10)
1. a kind of preparation method of dimer acid modified copolyester hot melt adhesive, which comprises the steps of:
(1) reaction kettle is added in the dimeric dibasic acid containing 36 carbon atoms, the dihydric alcohol containing 2-8 carbon atom and catalyst according to the ratio,
In 160-210 DEG C of completion esterification after mixing；
(2) thermoplastic polyester and stabilizer are added to the system after completing esterification in step (1), and are warming up to 250-260
DEG C, after reaction system becomes clear, constant temperature keeps 10-60min, is depressurized to 60-140Pa, polycondensation in 250-260 DEG C of constant temperature
1-4h discharges to after reaching required viscosity, and copolyester hot melt adhesive is made.
2. the preparation method of dimer acid modified copolyester hot melt adhesive as described in claim 1, which is characterized in that step (1)
The binary of fatty acids containing 6-18 carbon atom and the binary aromatic carboxylic acid containing 8 carbon atoms are additionally added in the reaction kettle.
3. the preparation method of dimer acid modified copolyester hot melt adhesive as claimed in claim 2, which is characterized in that the binary
Fatty acid be selected from 1,6- adipic acid, 1,8- suberic acid, 1,10- decanedioic acid, 1,12 dodecanedioic acid, 1,14- tetracosandioic acid,
One of octadecane diacid or several mixtures.
4. the preparation method of dimer acid modified copolyester hot melt adhesive as claimed in claim 2, which is characterized in that the binary
Aromatic carboxylic acids is terephthalic acid (TPA) or/and M-phthalic acid.
5. the preparation method of dimer acid modified copolyester hot melt adhesive as claimed in claim 2, which is characterized in that the binary
Alcohol is selected from ethylene glycol, 1,3- propylene glycol, 1,4- butanediol, 1,3 butylene glycol, 2- methyl-1,3-propanediol, 1,5- pentanediol, new
One of pentanediol, 1,6-HD, 1,4 cyclohexane dimethanol, diethylene glycol (DEG) or several compositions.
6. the preparation method of dimer acid modified copolyester hot melt adhesive as claimed in claim 2, which is characterized in that the binary
The molar ratio of fatty acid and the dihydric alcohol is 1:2.0~2.5.
7. the preparation method of dimer acid modified copolyester hot melt adhesive as claimed in claim 1 or 2, which is characterized in that described
Catalyst is selected from titanium system, tin class or antimony system, and the total dosage of catalyst is the binary of fatty acids and the dihydric alcohol quality summation
0.3%-1.5%.
8. the preparation method of dimer acid modified copolyester hot melt adhesive as claimed in claim 7, which is characterized in that the catalysis
Agent is butyl titanate.
9. the preparation method of dimer acid modified copolyester hot melt adhesive as claimed in claim 2, which is characterized in that the thermoplastic
Property polyester be selected from polyethylene terephthalate (PET), polypropylene terephthalate (PTT), poly terephthalic acid fourth
One or several kinds of combinations of diol ester (PBT), the total dosage of thermoplastic polyester are the binary of fatty acids and the dihydric alcohol matter
0.5-3.0 times for measuring summation.
10. the preparation method of dimer acid modified copolyester hot melt adhesive as claimed in claim 2, which is characterized in that described steady
Determining agent is triphenyl phosphite, and dosage is the 0.1%-1% of the binary of fatty acids and the dihydric alcohol quality summation.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810849720.3A CN108997570B (en) | 2018-07-28 | 2018-07-28 | Dimer acid modified copolyester hot melt adhesive and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810849720.3A CN108997570B (en) | 2018-07-28 | 2018-07-28 | Dimer acid modified copolyester hot melt adhesive and preparation method thereof |
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| CN108997570B CN108997570B (en) | 2020-09-15 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115109242A (en) * | 2022-07-14 | 2022-09-27 | 天津华新盈聚酯材料科技有限公司 | Low-melting-point polyester chip for producing antistatic milled hot melt adhesive and preparation method thereof |
| CN115232293A (en) * | 2022-07-14 | 2022-10-25 | 天津华新盈聚酯材料科技有限公司 | Low-melting-point polyester chip for producing milled hot melt adhesive and preparation method thereof |
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| CN1340585A (en) * | 2000-08-29 | 2002-03-20 | 上海理日科技发展有限公司 | Process for preparing polyester thermosol with high smelting point |
| CN102492388A (en) * | 2011-11-30 | 2012-06-13 | 上海天洋热熔胶有限公司 | High-melting-point polyester hot melt adhesive with better fluidity |
| CN103421460A (en) * | 2013-07-03 | 2013-12-04 | 上海天洋热熔胶有限公司 | Preparation method of crystalloid and transparent copolyester hot melt adhesive with high melting point |
| CN104629663A (en) * | 2013-11-11 | 2015-05-20 | 上海轻工业研究所有限公司 | Polyester hot melt adhesive |
| CN106189983A (en) * | 2016-07-27 | 2016-12-07 | 马爱芬 | A kind of footwear rapid link low melting point, high-adhesive-strength polyester hot-melt adhesive and its preparation method and application |
-
2018
- 2018-07-28 CN CN201810849720.3A patent/CN108997570B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1340585A (en) * | 2000-08-29 | 2002-03-20 | 上海理日科技发展有限公司 | Process for preparing polyester thermosol with high smelting point |
| CN102492388A (en) * | 2011-11-30 | 2012-06-13 | 上海天洋热熔胶有限公司 | High-melting-point polyester hot melt adhesive with better fluidity |
| CN103421460A (en) * | 2013-07-03 | 2013-12-04 | 上海天洋热熔胶有限公司 | Preparation method of crystalloid and transparent copolyester hot melt adhesive with high melting point |
| CN104629663A (en) * | 2013-11-11 | 2015-05-20 | 上海轻工业研究所有限公司 | Polyester hot melt adhesive |
| CN106189983A (en) * | 2016-07-27 | 2016-12-07 | 马爱芬 | A kind of footwear rapid link low melting point, high-adhesive-strength polyester hot-melt adhesive and its preparation method and application |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115109242A (en) * | 2022-07-14 | 2022-09-27 | 天津华新盈聚酯材料科技有限公司 | Low-melting-point polyester chip for producing antistatic milled hot melt adhesive and preparation method thereof |
| CN115232293A (en) * | 2022-07-14 | 2022-10-25 | 天津华新盈聚酯材料科技有限公司 | Low-melting-point polyester chip for producing milled hot melt adhesive and preparation method thereof |
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| CN108997570B (en) | 2020-09-15 |
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