CN109651605A - A kind of preparation method of biodegradable copolyester hot melt adhesive - Google Patents
A kind of preparation method of biodegradable copolyester hot melt adhesive Download PDFInfo
- Publication number
- CN109651605A CN109651605A CN201811517803.9A CN201811517803A CN109651605A CN 109651605 A CN109651605 A CN 109651605A CN 201811517803 A CN201811517803 A CN 201811517803A CN 109651605 A CN109651605 A CN 109651605A
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- hot melt
- preparation
- melt adhesive
- acid
- copolyester hot
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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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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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
- C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08G2170/00—Compositions for adhesives
- C08G2170/20—Compositions for hot melt adhesives
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention discloses a kind of preparation method of biodegradable copolyester hot melt adhesive, preparation step includes: that (1) will be mixed with M-phthalic acid by terephthalic acid (TPA) and form binary acid, with by 1,4- butanediol and polytetrahydrofuran ether glycol mixing composition dihydric alcohol, and catalyst, it is put by preset ratio and carries out esterification in esterifying kettle, 160 DEG C~225 DEG C of reaction temperature, when the amount for distillating water in esterifying kettle is 95% or more of theoretical water yield, esterification terminates；(2) antioxidant is added in the product of step (1), 230 DEG C~240 DEG C, 100Pa~150Pa under conditions of carry out polycondensation reaction 2.0h；(3) then logical nitrogen releases vacuum, discharges while hot to obtain the final product.Preparation step of the invention is easy, and prepares resulting copolyester hot melt adhesive through the invention, not only has biodegradable, but also have preferable adhesive effect.
Description
Technical field
The present invention relates to a kind of preparation method of copolyester hot melt adhesive, especially a kind of biodegradable copolyesters hot melt
The preparation method of glue.
Background technique
Each hot melt adhesive has been widely used in the compound sticking of multiple fields, such as weave lining cloth, food packaging, footwear material and
The packaging joint sealing etc. of medicine.In the production preparation process of hot melt adhesive, its adhesive property is only considered in the past, without considering its degradation
Performance.In recent years, with hot melt adhesive dosage increase substantially and the gradually enhancing of people's environmental consciousness, conventional hot melt glue is because of it
Architectural characteristic, it is strong to the resistance of microorganism, it is difficult to degrade, the environmental issue being present in natural environment is also increasingly prominent.Therefore
The good and biodegradable environment-friendly type hot melt glue of adhesive effect is prepared in production, becomes the important development direction of adhesive industry.
Biodegradable hot melt adhesive, biological degradability are completed by hydrolysis and oxidation.It is main at present
Biodegradable PUR has natural polymer subtype, poly lactic acid type, polyesteramide type and copolymerization ester type.Wherein, wherein can biology
The copolymerization ester type hot melt adhesive of degradability, preparation step are generally complex.As US5889135 discloses a kind of fat/aromatic series
Polyester, it is that aliphatic acid and 1,4-butanediol are carried out esterification under tin compound effect, then again by terephthaldehyde
Dimethyl phthalate and 1,4-butanediol carry out ester exchange reaction under titanium compound effect, and esterification and transesterification product contract together
Poly- reaction；CN200980113152.X proposes one kind by polycaprolactone, dicarboxylic acids and dihydric alcohol polycondensation and by terpenes tree
The modified composition adhesive thermofusible biodegradable obtained such as rouge.
Therefore how the copolymerization ester type hot melt adhesive that a kind of preparation step is easy, biodegradable is provided, become to be solved
Problem.
Summary of the invention
It is an object of the invention to solve above-mentioned technical problem, a kind of system of biodegradable copolyester hot melt adhesive is proposed
Preparation Method, preparation step of the invention is easy, and prepares resulting copolyester hot melt adhesive through the invention, and both having had biological can drop
Xie Xing, and there is preferable adhesive effect.
The technical scheme adopted by the invention is as follows: a kind of preparation method of biodegradable copolyester hot melt adhesive, step
It is as follows:
(1) it by binary acid and dihydric alcohol, catalyst, is put by preset ratio and carries out esterification, reaction temperature in esterifying kettle
160 DEG C~225 DEG C, when the amount for distillating water in esterifying kettle is 95% or more of theoretical water yield, esterification terminates；
(2) antioxidant is added in the product of step (1), 230 DEG C~240 DEG C, 100Pa~150Pa under conditions of carry out
Polycondensation reaction 2.0h；
(3) then logical nitrogen releases vacuum, discharges while hot to obtain the final product.
In above-mentioned steps (1), binary acid is mixed with M-phthalic acid by terephthalic acid (TPA) and is formed；Dihydric alcohol is then by 1,4- fourth
Two pure and mild polytetrahydrofuran ether glycol mixing compositions.
The proportion of each material is as follows:
Binary acid: the molar ratio of dihydric alcohol is 1:1.5；
In binary acid, terephthalic acid (TPA): the molar ratio of M-phthalic acid is 0.5 ~ 0.6:0.4 ~ 0.5；
In dihydric alcohol, 1,4-butanediol: the molar ratio of polytetrahydrofuran ether glycol is 0.9 ~ 0.95:0.05 ~ 0.1.
Above-mentioned catalyst is tetraisopropyl titanate, and additional amount is the 0.008% of binary acid gross mass；
The trade mark of above-mentioned antioxidant is 1010 or 168, and additional amount is the 0.5% of binary acid gross mass.
Innovation of the invention is: devising unique raw material and proportion, especially creative introduces poly- four
Hydrogen furans ether glycol, improves the interaction force between product molecule chain, enhances the cohesive strength of product；Meanwhile to production
The dosage of the material system of object is defined, especially the dosage of polytetrahydrofuran ether glycol, reach equilibrium products can biology
The purpose of decomposability and adhesive effect.The beneficial effects of the present invention are: preparation step of the invention is easy, and a step is esterified a step
Condensation polymerization step completes reaction；Meanwhile resulting copolyester hot melt adhesive is prepared through the invention, having biodegradable
Under the premise of, there is preferable adhesive effect.
Specific embodiment
The present invention is addressed further under below by embodiment, but is not limited thereto.
Embodiment 1:
A kind of preparation method of copolyester hot melt adhesive, preparation step are as follows:
(1) binary acid that will be made of terephthalic acid (TPA) 99.6g, M-phthalic acid 66.4g, and by 1,4-butanediol 128.3g,
The dihydric alcohol and catalyst tetraisopropyl titanate 0.13g of polytetrahydrofuran ether glycol 75g composition, 160 DEG C of reaction temperature~
225 DEG C, when the amount for distillating water in esterifying kettle is 95% or more of theoretical water yield, esterification terminates；
(2) by the trade mark be 1010 antioxidant 0.83g be added in the product of step (1), 230 DEG C~240 DEG C, 100Pa~
Polycondensation reaction 2.0h is carried out under conditions of 150Pa；
(3) lead to nitrogen and release vacuum, discharge while hot to obtain the final product.
A1 is labeled as by 1 products therefrom sample of embodiment.
Embodiment 2:
A kind of preparation method of copolyester hot melt adhesive, preparation step are as follows:
(1) binary acid that will be made of terephthalic acid (TPA) 83g, M-phthalic acid 83g, and by 1,4-butanediol 128.3g, poly- four
The dihydric alcohol and catalyst tetraisopropyl titanate 0.13g of hydrogen furans ether glycol 75g composition, 160 DEG C~225 DEG C of reaction temperature,
When the amount for distillating water in esterifying kettle is 95% or more of theoretical water yield, esterification terminates；
(2) by the trade mark be 168 antioxidant 0.83g be added in the product of step (1), 230 DEG C~240 DEG C, 100Pa~
Polycondensation reaction 2.0h is carried out under conditions of 150Pa；
(3) lead to nitrogen and release vacuum, discharge while hot to obtain the final product.
A2 is labeled as by 2 products therefrom sample of embodiment.
Embodiment 3:
A kind of preparation method of copolyester hot melt adhesive, preparation step are as follows:
(1) binary acid that will be made of terephthalic acid (TPA) 99.6g, M-phthalic acid 66.4g, and by 1,4-butanediol 121.5g,
The dihydric alcohol and catalyst tetraisopropyl titanate 0.13g of polytetrahydrofuran ether glycol 150g composition, 160 DEG C of reaction temperature~
225 DEG C, when the amount for distillating water in esterifying kettle is 95% or more of theoretical water yield, esterification terminates；
(2) by the trade mark be 168 antioxidant 0.83g be added in the product of step (1), 230 DEG C~240 DEG C, 100Pa~
Polycondensation reaction 2.0h is carried out under conditions of 150Pa；
(3) lead to nitrogen and release vacuum, discharge while hot to obtain the final product.
A3 is labeled as by 3 products therefrom sample of embodiment.
Embodiment 4:
A kind of preparation method of copolyester hot melt adhesive, preparation step are as follows:
(1) binary acid that will be made of terephthalic acid (TPA) 83g, M-phthalic acid 83g, and by 1,4-butanediol 121.5g, poly- four
The dihydric alcohol and catalyst tetraisopropyl titanate 0.13g of hydrogen furans ether glycol 150g composition, reaction temperature 160 DEG C~225
DEG C, when the amount for distillating water in esterifying kettle is 95% or more of theoretical water yield, esterification terminates；
(2) by the trade mark be 168 antioxidant 0.83g be added in the product of step (1), 230 DEG C~240 DEG C, 100Pa~
Polycondensation reaction 2.0h is carried out under conditions of 150Pa；
(3) lead to nitrogen and release vacuum, discharge while hot to obtain the final product.
A4 is labeled as by 4 products therefrom sample of embodiment.
Embodiment 5:
A kind of preparation method of copolyester hot melt adhesive, preparation step are as follows:
(1) binary acid that will be made of terephthalic acid (TPA) 91.3g, M-phthalic acid 74.7g, and by 1,4-butanediol 126.5g,
The dihydric alcohol and catalyst tetraisopropyl titanate 0.13g of polytetrahydrofuran ether glycol 105g composition, 160 DEG C of reaction temperature~
225 DEG C, when the amount for distillating water in esterifying kettle is 95% or more of theoretical water yield, esterification terminates；
(2) by the trade mark be 1010 antioxidant 0.83g be added in the product of step (1), 230 DEG C~240 DEG C, 100Pa~
Polycondensation reaction 2.0h is carried out under conditions of 150Pa；
(3) lead to nitrogen and release vacuum, discharge while hot to obtain the final product.
A5 is labeled as by 5 products therefrom sample of embodiment.
Sample A1 ~ A5 obtained by the various embodiments described above is subjected to following test:
1, biodegradability: reference standard EN/ISO 14855, according to release carboloy dioxide analysis method measurement.Corresponding percentage
Than being provided with reference to the biodegradability of cellulose, the biodegradability of cellulose is 100% under the same conditions；
2, peel strength test: GB/T 11402 is referred to.
Described in test result is as follows table 1:
| [0001] it marks | [0002] biological degradability | [0003] peel strength (N/5cm) |
| [0004] A1 | [0005] 65% | [0006] 19.2 |
| [0007] A2 | [0008] 59% | [0009] 21.3 |
| [0010] A3 | [0011] 55% | [0012] 22.0 |
| [0013] A4 | [0014] 70% | [0015] 19.8 |
| [0016] A5 | [0017] 60% | [0018] 20.5 |
Table 1: performance test table.
Claims (5)
1. a kind of preparation method of biodegradable copolyester hot melt adhesive, which comprises the steps of:
(1) it will be mixed by terephthalic acid (TPA) with M-phthalic acid and form binary acid, and by 1,4-butanediol and polytetrahydrofuran ether
Glycol mixing composition dihydric alcohol and catalyst, are put by preset ratio and carry out esterification, reaction temperature in esterifying kettle
160 DEG C~225 DEG C, when the amount for distillating water in esterifying kettle is 95% or more of theoretical water yield, esterification terminates；
(2) antioxidant is added in the product of step (1), 230 DEG C~240 DEG C, 100Pa~150Pa under conditions of carry out
Polycondensation reaction 2.0h；
(3) then logical nitrogen releases vacuum, discharges while hot to obtain the final product；
The proportion of each material is as follows:
Binary acid: the molar ratio of dihydric alcohol is 1:1.5；
In binary acid, terephthalic acid (TPA): the molar ratio of M-phthalic acid is 0.5 ~ 0.6:0.4 ~ 0.5；
In dihydric alcohol, 1,4-butanediol: the molar ratio of polytetrahydrofuran ether glycol is 0.9 ~ 0.95:0.05 ~ 0.1.
2. the preparation method of biodegradable copolyester hot melt adhesive as described in claim 1, it is characterised in that: the catalysis
Agent is tetraisopropyl titanate.
3. the preparation method of biodegradable copolyester hot melt adhesive as claimed in claim 2, it is characterised in that: the catalysis
The additional amount of agent is the 0.008% of binary acid gross mass.
4. the preparation method of biodegradable copolyester hot melt adhesive as described in claim 1, it is characterised in that: the antioxygen
The trade mark of agent is 1010 or 168.
5. the preparation method of biodegradable copolyester hot melt adhesive as claimed in claim 4, it is characterised in that: the antioxygen
The additional amount of agent is the 0.5% of binary acid gross mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811517803.9A CN109651605A (en) | 2018-12-12 | 2018-12-12 | A kind of preparation method of biodegradable copolyester hot melt adhesive |
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| CN201811517803.9A CN109651605A (en) | 2018-12-12 | 2018-12-12 | A kind of preparation method of biodegradable copolyester hot melt adhesive |
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| CN109651605A true CN109651605A (en) | 2019-04-19 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113576767A (en) * | 2021-07-30 | 2021-11-02 | 广东茵茵股份有限公司 | Reinforced structure paper diaper with composite core |
| CN113576768A (en) * | 2021-07-30 | 2021-11-02 | 广东茵茵股份有限公司 | Degradable baby diaper |
| CN114181654A (en) * | 2021-12-21 | 2022-03-15 | 上海东睿化学有限公司 | Biodegradable copolyester hot melt adhesive and preparation method thereof |
| CN114318585A (en) * | 2021-12-24 | 2022-04-12 | 余姚大发化纤有限公司 | High-elasticity thermal-bonding composite polyester fiber, preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4097548A (en) * | 1977-06-23 | 1978-06-27 | The Goodyear Tire & Rubber Company | Polyester-containing hot melt adhesive composition |
| JPS56146723A (en) * | 1980-04-16 | 1981-11-14 | Kuraray Co Ltd | Preparation of film |
| JPH01299883A (en) * | 1988-05-27 | 1989-12-04 | Kuraray Co Ltd | Hot melt adhesive |
| CN103012761A (en) * | 2012-12-05 | 2013-04-03 | 金发科技股份有限公司 | Method for preparing copolyether ester elastomer |
| CN103102646A (en) * | 2011-11-09 | 2013-05-15 | 金发科技股份有限公司 | Low-melting point and high-crystallization temperature PET copolyester, its preparation method and application |
| CN104927037A (en) * | 2015-05-28 | 2015-09-23 | 上海天洋热熔粘接材料股份有限公司 | Preparation method of polyester hot melt adhesive applicable to powder-point-method low-temperature sizing |
-
2018
- 2018-12-12 CN CN201811517803.9A patent/CN109651605A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4097548A (en) * | 1977-06-23 | 1978-06-27 | The Goodyear Tire & Rubber Company | Polyester-containing hot melt adhesive composition |
| JPS56146723A (en) * | 1980-04-16 | 1981-11-14 | Kuraray Co Ltd | Preparation of film |
| JPH01299883A (en) * | 1988-05-27 | 1989-12-04 | Kuraray Co Ltd | Hot melt adhesive |
| CN103102646A (en) * | 2011-11-09 | 2013-05-15 | 金发科技股份有限公司 | Low-melting point and high-crystallization temperature PET copolyester, its preparation method and application |
| CN103012761A (en) * | 2012-12-05 | 2013-04-03 | 金发科技股份有限公司 | Method for preparing copolyether ester elastomer |
| CN104927037A (en) * | 2015-05-28 | 2015-09-23 | 上海天洋热熔粘接材料股份有限公司 | Preparation method of polyester hot melt adhesive applicable to powder-point-method low-temperature sizing |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113576767A (en) * | 2021-07-30 | 2021-11-02 | 广东茵茵股份有限公司 | Reinforced structure paper diaper with composite core |
| CN113576768A (en) * | 2021-07-30 | 2021-11-02 | 广东茵茵股份有限公司 | Degradable baby diaper |
| CN113576767B (en) * | 2021-07-30 | 2022-05-31 | 广东茵茵股份有限公司 | Reinforced structure paper diaper with composite core |
| CN114181654A (en) * | 2021-12-21 | 2022-03-15 | 上海东睿化学有限公司 | Biodegradable copolyester hot melt adhesive and preparation method thereof |
| CN114318585A (en) * | 2021-12-24 | 2022-04-12 | 余姚大发化纤有限公司 | High-elasticity thermal-bonding composite polyester fiber, preparation method and application |
| CN114318585B (en) * | 2021-12-24 | 2024-03-08 | 余姚大发化纤有限公司 | High-elasticity thermal-bonding composite polyester fiber, preparation method and application |
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Application publication date: 20190419 |