CN103468195A - Preparation method of biodegradable polyester hot melt adhesive - Google Patents
Preparation method of biodegradable polyester hot melt adhesive Download PDFInfo
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- CN103468195A CN103468195A CN2013104421221A CN201310442122A CN103468195A CN 103468195 A CN103468195 A CN 103468195A CN 2013104421221 A CN2013104421221 A CN 2013104421221A CN 201310442122 A CN201310442122 A CN 201310442122A CN 103468195 A CN103468195 A CN 103468195A
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Abstract
The invention discloses a preparation method of a biodegradable polyester hot melt adhesive, which mainly comprises the following steps: (1) adding an aliphatic dibasic acid, 1,4-butanediol and other dibasic alcohols, and a catalyst into a reactor, and carrying out an esterification reaction on the obtained mixture under the protection of nitrogen, wherein the reaction temperature is 120-220 DEG C, and the gas phase temperature is kept at about 98 DEG C; and after the distillate quantity of water is over 95% of a theoretical quantity, completing the esterification reaction; (2) adding a phosphite ester stabilizer and grapheme into the obtained mixture, continuing to heat the obtained mixture to 210-230 DEG C, then carrying out a decompressed polycondensation reaction on the obtained mixture for 0.5-1.5 h so as to obtain a random copolymer, and freezing and crushing the random copolymer so as to obtain copolymer powder.
Description
Technical field
The present invention relates to a kind of preparation method of biodegradable polyesters hot melt adhesive.
Background technology
In the production of hot melt adhesive, the past is generally only considered its adhesiveproperties, and does not consider its degradation property.In recent years, along with increasing substantially of the consumption of hot melt adhesive, the problem of its initiation also shows especially day by day.Produce the matrix resin of hot melt adhesive the most frequently used ethene and the polymer organism such as multipolymer, copolyesters, copolyamide, vinylbenzene and segmented copolymer thereof thereof are arranged; due to its structural performance; making it can not be the microbiological deterioration in environment or hydrolysis, therefore can bring many unfavorable factors to protection and the closed matereial cycle of environment.Along with the enhancing of increasingly sound and people's environmental consciousness of environmental regulation, the good and degradable environment-friendly hot melt adhesive of production bonding strength has become the important development direction of adhesive industry.
Known biodegradable hot melt adhesive all adopts blending and modifying or natural polymer to make at present, as Japanese Patent JP2003020463 be take the starch paste as the natural polymer base-material, with other auxiliary agent copolymerization biodegradable hot melt adhesives such as appropriate softening agent, stablizers.As Chinese patent CN 102007192A discloses a kind of polycaprolactone, di-carboxylic acid and dibasic alcohol polycondensation and has made a kind of composition adhesive thermofusible biodegradable by modifications such as terpine resins.As Chinese patent 200810035583.6 provides a kind of preparation method of full biodegradable environment protection hot melt adhesive of modification of corn starch.
But, from prior art, the biodegradable hot melt adhesive of producing is all to obtain by the blending and modifying means, does not have a kind of synthesis preparation method of technical specification biodegradable polyesters hot melt adhesive.Patent of the present invention aims to provide a kind of synthesis preparation method of biodegradable copolyester hot melt adhesive.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of biodegradable copolyester hot melt adhesive, prepared biodegradable polyesters hot melt adhesive, have that fusing point is low, crystallization is fast, preparation technology is simple.
Method of the present invention comprises the steps:
(1) aliphatic dibasic acid, BDO and other dibasic alcohol, catalyzer are added to reactor, carry out esterification under nitrogen protection, temperature of reaction is 120 ~ 220 ℃, gas phase temperature is maintained at about 98 ℃, react to the quantity of distillate of water be theoretical amount more than 95%, esterification completes;
(2) add stablizer and filler, continue to be warming up to 210 ~ 230 ℃ of polycondensation 0.5 ~ 1.5h that reduced pressure, obtain random copolymers, then, through freezing, pulverize, can obtain copolymer powder;
Described aliphatic dibasic acid is 1,6-hexanodioic acid, 1, 4-succinic acid, 1,10-sebacic acid, 1,12-dodecanedioic acid, 1, more than one in 14-14 diacid;
Described other dibasic alcohol are Diethylene Glycol, ethylene glycol, polyoxyethylene glycol, 1,6-hexylene glycol, 1,3-PD, 2,2,4-trimethylammonium-1, a kind of in the 3-pentanediol;
Mol ratio between described other dibasic alcohol and BDO is 0.05 ~ 0.8: 1;
The mol ratio of described total acid and total alcohol is 1
:1.1 ~ 1.8, described total acid refers to the summation of all aliphatic dibasic acids used, described total alcohol refers to the summation of BDO and other dibasic alcohol;
The mixture that described catalyzer is tin protochloride, Phenylsulfonic acid and tetrabutyl titanate, the consumption of tin protochloride is 0.02% ~ 0.04% of total acid quality, the consumption of Phenylsulfonic acid is 0.02% ~ 0.04% of total acid quality, and the consumption of tetrabutyl titanate is 0.02% ~ 0.04% of total acid quality.
Described filler is Graphene, and its consumption is theoretical load 0.01% ~ 10%.
Described stablizer is triphenyl phosphite, and its consumption is 0.01% ~ 0.09% of total acid quality.
Innovation of the present invention is to synthesize a kind of biodegradable polyester hot-melt adhesive by melt intercalated method, realizes the needs of environmental friendliness, low melting point, nontoxic condition.
specific implementation method
Below by specific embodiment, the invention will be further elaborated, but the present invention is not limited to these embodiment.
embodiment 1
In the four-hole boiling flask with thermometer, mechanical stirrer, reflux condensing tube, add 1,6-hexanodioic acid 73.0g, 1,4-succinic acid 59.0g, BDO 102.6g, 1,6-hexylene glycol 7.08g, tin protochloride 2.64mg, Phenylsulfonic acid 2.64mg, tetrabutyl titanate 2.64mg, logical nitrogen, heating, and stir, open water of condensation, when reactor temperature reaches 140 ℃ of left and right, start to have water to distill out, at the uniform velocity heat up, wait the water steamed, reach 95% when above of theoretical amount, esterification completes.Insulation 0.5h, continue to be warming up to 220 ℃, and add triphenyl phosphite 0.013g in above-mentioned reaction system, Graphene 0.017g, decompression gradually, until system pressure 100Pa, reaction times 30min, temperature is increased to 230 ℃ gradually by 220 ℃, and polycondensation completes.Remove vacuum state under nitrogen protection, obtain copolymer particle, then, through freezing, pulverize, can obtain the blocked copolyester powder.Measuring this product molecular-weight average with gel permeation chromatography and DSC respectively is 25260g/mol, and fusing point is: 102-112 ℃ records its melt flow rate (MFR) by GB GB/T3682-2000 and is: 120g/10min160 ℃.
Embodiment 2-6
Step and the processing condition of embodiment 2-6 and embodiment 1 are basic identical, and processing condition and the proportioning raw materials of having some change are as shown in table 1, and the performance of products therefrom is also listed in table 1.
Table 1 embodiment 2-6 related process parameter and product property
| No. embodiment | 2 | 3 | 4 |
| 1,6-hexanodioic acid | 73.0 | 99.28 | 73.0 |
| 1,10-sebacic acid | ? | 64.64 | ? |
| 1,12-dodecanedioic acid | 114 | ? | ? |
| 1,14-tetradecane diacid | ? | ? | ? |
| 1, 4-succinic acid, g | ? | ? | 59.0 |
| BDO, g | 153.9 | 114.8 | 153.9 |
| 1,6-hexylene glycol, g | ? | ? | 36.0 |
| Diethylene Glycol, g | ? | 23.85 | ? |
| Polyoxyethylene glycol, g | 36.0 | ? | ? |
| Tetrabutyl titanate, mg | 748 | 264 | 325 |
| Phenylsulfonic acid, mg | 748 | 264 | 264 |
| Tin protochloride, mg | 264 | 264 | 264 |
| Triphenyl phosphite, g | 0.168 | 0.023 | 0.078 |
| Graphene, g | 0.17 | 0.08 | 0.12 |
| The esterification soaking time, min | 100 | 120 | 150 |
| The polycondensation time, min | 90 | 50 | 65 |
| Condensation temperature, ℃ | 210 | 220 | 230 |
| Molecular-weight average | 36240 | 20830 | 28050 |
| Fusing point, ℃ | 98~112 | 104~116 | 102-109 |
| Melting index, g/10min (160 ℃) | 95.7 | 88.3 | 84.7 |
Claims (4)
1. the preparation method of a biodegradable polyesters hot melt adhesive, is characterized in that comprising the steps:
(1) aliphatic dibasic acid, BDO and other dibasic alcohol, catalyzer are added to reactor, carry out esterification under nitrogen protection, temperature of reaction is 120 ~ 220 ℃, gas phase temperature is maintained at about 98 ℃, react to the quantity of distillate of water be theoretical amount more than 95%, esterification completes;
(2) add stablizer and filler, continue to be warming up to 210 ~ 230 ℃ of polycondensation 0.5 ~ 1.5h that reduced pressure, obtain random copolymers, then, through freezing, pulverize, can obtain copolymer powder;
Described aliphatic dibasic acid is 1,6-hexanodioic acid, 1, 4-succinic acid, 1,10-sebacic acid, 1,12-dodecanedioic acid, 1, more than one in 14-14 diacid;
Described other dibasic alcohol are Diethylene Glycol, ethylene glycol, polyoxyethylene glycol, 1,6-hexylene glycol, 1,3-PD, 2,2,4-trimethylammonium-1, a kind of in the 3-pentanediol;
Mol ratio between described other dibasic alcohol and BDO is 0.05 ~ 0.8: 1;
The mol ratio of described total acid and total alcohol is 1
:1.1 ~ 1.8, described total acid refers to the summation of all aliphatic dibasic acids used, described total alcohol refers to the summation of BDO and other dibasic alcohol.
2. method according to claim 1, it is characterized in that the mixture that described catalyzer is tin protochloride, Phenylsulfonic acid and tetrabutyl titanate, the consumption of tin protochloride is 0.02% ~ 0.04% of total acid quality, the consumption of Phenylsulfonic acid is 0.02% ~ 0.04% of total acid quality, and the consumption of tetrabutyl titanate is 0.02% ~ 0.04% of total acid quality.
3. method according to claim 1, is characterized in that, described filler is Graphene, and its consumption is theoretical load 0.01% ~ 10%.
4. method according to claim 1, is characterized in that, described stablizer is triphenyl phosphite, and its consumption is 0.01% ~ 0.09% of total acid quality.
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| CN2013104421221A CN103468195A (en) | 2013-09-26 | 2013-09-26 | Preparation method of biodegradable polyester hot melt adhesive |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106318305A (en) * | 2016-08-30 | 2017-01-11 | 上海天洋热熔粘接材料股份有限公司 | Polyester hot melt adhesive for film preparation and preparation method of polyester hot melt adhesive |
| CN107652420A (en) * | 2017-09-22 | 2018-02-02 | 昆山天洋热熔胶有限公司 | A kind of preparation method of biodegradable copolyester hot melt adhesive |
| CN112661947A (en) * | 2020-12-22 | 2021-04-16 | 上海华峰新材料研发科技有限公司 | Polyester polyol and preparation method and application thereof |
| WO2023229310A1 (en) * | 2022-05-23 | 2023-11-30 | 에코밴스 주식회사 | Biodegradable polyester polymer composition, biodegradable polyester resin using same, and preparation method thereof |
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| CN1088945A (en) * | 1992-12-24 | 1994-07-06 | 株式会社鲜京工业 | Thermoplasticity Biodegradable resin and preparation method thereof |
| CN101245230A (en) * | 2008-02-21 | 2008-08-20 | 上海天洋热熔胶有限公司 | Method for manufacturing linear copolyester hot melt adhesive |
| CN102229702A (en) * | 2011-05-11 | 2011-11-02 | 浙江比例包装股份有限公司 | Production method of complete biodegradable aliphatic polyester |
| CN102690409A (en) * | 2012-06-16 | 2012-09-26 | 上海天洋热熔胶有限公司 | Method for preparing low-melting-point polyester hot melt adhesive |
| CN103145960A (en) * | 2013-03-25 | 2013-06-12 | 山东汇盈新材料科技有限公司 | Aliphatic-aromatic copolyester and preparation method thereof |
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2013
- 2013-09-26 CN CN2013104421221A patent/CN103468195A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1088945A (en) * | 1992-12-24 | 1994-07-06 | 株式会社鲜京工业 | Thermoplasticity Biodegradable resin and preparation method thereof |
| CN101245230A (en) * | 2008-02-21 | 2008-08-20 | 上海天洋热熔胶有限公司 | Method for manufacturing linear copolyester hot melt adhesive |
| CN102229702A (en) * | 2011-05-11 | 2011-11-02 | 浙江比例包装股份有限公司 | Production method of complete biodegradable aliphatic polyester |
| CN102690409A (en) * | 2012-06-16 | 2012-09-26 | 上海天洋热熔胶有限公司 | Method for preparing low-melting-point polyester hot melt adhesive |
| CN103145960A (en) * | 2013-03-25 | 2013-06-12 | 山东汇盈新材料科技有限公司 | Aliphatic-aromatic copolyester and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106318305A (en) * | 2016-08-30 | 2017-01-11 | 上海天洋热熔粘接材料股份有限公司 | Polyester hot melt adhesive for film preparation and preparation method of polyester hot melt adhesive |
| CN106318305B (en) * | 2016-08-30 | 2021-08-10 | 上海天洋热熔粘接材料股份有限公司 | Preparation method of polyester hot melt adhesive for film making |
| CN107652420A (en) * | 2017-09-22 | 2018-02-02 | 昆山天洋热熔胶有限公司 | A kind of preparation method of biodegradable copolyester hot melt adhesive |
| CN107652420B (en) * | 2017-09-22 | 2019-08-09 | 昆山天洋热熔胶有限公司 | A kind of preparation method of biodegradable copolyester hot melt adhesive |
| CN112661947A (en) * | 2020-12-22 | 2021-04-16 | 上海华峰新材料研发科技有限公司 | Polyester polyol and preparation method and application thereof |
| WO2023229310A1 (en) * | 2022-05-23 | 2023-11-30 | 에코밴스 주식회사 | Biodegradable polyester polymer composition, biodegradable polyester resin using same, and preparation method thereof |
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Application publication date: 20131225 |