CN105061741A - Water-boiling-resistant polyester resin and preparation method thereof - Google Patents

Water-boiling-resistant polyester resin and preparation method thereof Download PDF

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Publication number
CN105061741A
CN105061741A CN201510566369.3A CN201510566369A CN105061741A CN 105061741 A CN105061741 A CN 105061741A CN 201510566369 A CN201510566369 A CN 201510566369A CN 105061741 A CN105061741 A CN 105061741A
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China
Prior art keywords
water boiling
preparation
boiling resistance
acid
vibrin
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Pending
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CN201510566369.3A
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Chinese (zh)
Inventor
宋瑾
张明
钱永嘉
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CHANGZHOU HUAKE RESIN Co Ltd
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CHANGZHOU HUAKE RESIN Co Ltd
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Abstract

The invention relates to water-boiling-resistant polyester resin and a preparation method thereof. The resin is obtained by performing condensation polymerization on small-molecule dibasic acid or anhydride, small-molecule dibasic alcohol, organic polyol and polycarbonate diol in the presence of an esterification catalyst. By virtue of polymerization reaction, carbonate bonds are introduced into the structure of the water-boiling-resistant polyester resin, so that excellent wear resistance and durability are provided for a water-boiling-resistant coating, and meanwhile, the water boiling resistance of the resin is not influenced; and moreover, the raw materials adopted by the polymerization reaction are low in price and easy to obtain, the preparation method is simple and easy to operate, reasonable in process design, and suitable for large-scale industrial production.

Description

A kind of water boiling resistance vibrin and preparation method thereof
Technical field
The present invention relates to a kind of vibrin, particularly a kind of water boiling resistance vibrin and preparation method thereof.
Background technology
Along with the standard of living of the people improves, also more and more higher to the requirement of the comfort level of home decoration and sanitaryware, so also strengthen gradually the concern of water boiling resistance coating and demand.For the market requirement that this is special, repeatedly practise and prove common water boiling resistance vibrin to be applied in relevant coating, find water boiling resistance excellent property but weather resistance and wear resistance also exist larger deficiency.
Chinese patent application CN101735431 discloses weather resistant vibrin of a kind of water boiling resistance excellent performance and preparation method thereof, and this vibrin is obtained through polycondensation by polyvalent alcohol, aromatic polycarboxylic acid, sour, the branching agent of aliphatic polyol, acidolysis agent, esterifying catalyst.Its weather resistant is improved to some extent, but the wear resistance of vibrin is not improved.
The intermolecular force of cohesion of carbonic acid ester bond is comparatively strong, has higher second-order transition temperature and fusing point, compared with polyester key, has good wear resistance and weather resistance.
Summary of the invention
The object of the invention is: in order to solve the problem, the invention provides a kind of water boiling resistance vibrin and preparation method thereof, carbonic acid ester bond is introduced in common water boiling resistance vibrin segment, under the prerequisite not affecting its water boiling resistance performance, substantially increase wear resistance and the weather resistance of water boiling resistance vibrin.
The technical scheme realizing the object of the invention is: a kind of water boiling resistance vibrin, and this resin prepares by the following method: by small molecules diprotic acid (acid anhydride), small molecules dibasic alcohol, organic polyhydric alcohol and polycarbonate diol carry out polycondensation.
Be specially following steps:
Small molecules dibasic alcohol, organic polyhydric alcohol are added in the reactor with heat riser and whipping appts; pass into nitrogen; intensification is heated to material and melts as liquid; add small molecules diprotic acid (acid anhydride), polycarbonate diol and esterifying catalyst more successively; continue under nitrogen protection to be warming up to water outlet; heat up in a steamer a temperature: 90-103 DEG C, temperature of reaction: 140-230 DEG C, preferably 200 DEG C, 205 DEG C, 210 DEG C, 215 DEG C, 220 DEG C, 225 DEG C, 230 DEG C.Reaction is to target acid number: 3-6mgKOH/g, and target Cone & Plate viscosity (175 DEG C): 10-13P, stopped reaction, can obtain the endurable polyester resin of water boiling resistance excellent performance.
The preparation method of above-mentioned water boiling resistance vibrin, described alkyd equivalence ratio is (1.1-1.3): 1 feeds intake, and preferred 1.15:1 or 1.2:1 or 1.3:1 feeds intake.
The preparation method of above-mentioned water boiling resistance vibrin, one in described esterifying catalyst tetrabutyl titanate, titanium isopropylate, lithium hydroxide, lead acetate, Dibutyltin oxide or Mono-n-butyltin, catalyzer is preferably lithium hydroxide or Dibutyltin oxide or Mono-n-butyltin.
The preparation method of above-mentioned water boiling resistance vibrin, described small molecules diprotic acid (acid anhydride) is preferably Tetra hydro Phthalic anhydride, m-phthalic acid, terephthalic acid, one or more in hexanodioic acid.
The preparation method of above-mentioned water boiling resistance vibrin, described small molecules dibasic alcohol is preferably methyl propanediol, BDO, in 1.6-hexylene glycol, ethylene glycol, glycol ether, neopentyl glycol one or more.
The preparation method of above-mentioned water boiling resistance vibrin, described organic polyhydric alcohol is preferably TriMethylolPropane(TMP) or trimethylolethane.
The preparation method of above-mentioned water boiling resistance vibrin, described polycarbonate diol is UH-CARB50, UM-CARB90 (3/1) of Ube company, one or more of UM-CARB90 (1/1), more preferably UH-CARB50.
A kind of water boiling resistance vibrin, it is by the polymkeric substance formed after small molecules diprotic acid (acid anhydride), small molecules dibasic alcohol, organic polyhydric alcohol and polycarbonate diol polycondensation, is the product prepared by above-mentioned either method.
The present invention is based upon on the basis of environmental protection theory, through extensive and deep research, by the water boiling resistance vibrin formed after small molecules diprotic acid (acid anhydride), small molecules dibasic alcohol, organic polyhydric alcohol and polycarbonate diol polycondensation, the rosin products obtained is because having excellent water boiling resistance performance, antifriction scrape along weather resistance containing carbonic acid ester bond.
The present invention has positive effect: (1) the present invention introduces carbonic acid ester bond by polyreaction in water boiling resistance polyester resin structure, for water boiling resistance coating provides excellent wear resistance and weather resistance, does not affect the water boiling resistance performance of this resin simultaneously; (2) the present invention chooses most suitable temperature of reaction, reacts completely; (3) raw material that adopts of polyreaction of the present invention is all cheap is easy to get, and preparation method is simple to operation, and technological design is reasonable, is applicable to large-scale industrial production.
Embodiment
(embodiment 1)
In the reactor with agitator, temperature rising reflux device, add 400.6g methyl propanediol, 450.7g1,4-butyleneglycol and 272.8g TriMethylolPropane(TMP) open and stir and pass into nitrogen, be warming up to 60-80 DEG C and melt as liquid to material.Add 456.2g Tetra hydro Phthalic anhydride, 734.8g m-phthalic acid, 364.9g hexanodioic acid, 170gUH-CARB50 and 2.5g Mono-n-butyltin again.Be warming up to water outlet under nitrogen protection, heat up in a steamer a temperature 90-103 DEG C, according to heating up in a steamer a temperature to maximum temperature 220 DEG C; sampling and testing resinous acid value: 4.2mgKOH/g, when 175 DEG C of cone-plates glue for 10.9P, stopped reaction; be cooled to rapidly 90 DEG C of dischargings, obtain target water boiling resistance vibrin.Wherein alkyd feed ratio is 1.15:1.
The water boiling resistance vibrin of above-mentioned preparation, flow agent, other additives, solidifying agent are prepared water boiling resistance coating through high speed dispersion.
(embodiment 2)
In the reactor with agitator, temperature rising reflux device, add 262.5g ethylene glycol, 507.4g1,6-hexylene glycol and 639.2g tetramethylolmethane open and stir and pass into nitrogen, be warming up to 60-80 DEG C and melt as liquid to material.Add 412g Tetra hydro Phthalic anhydride, 778g m-phthalic acid, 700g sebacic acid, 250gUH-CARB90 (3/1) and 3.5g lithium hydroxide again.Be warming up to water outlet under nitrogen protection, heat up in a steamer a temperature 90-103 DEG C, according to heating up in a steamer a temperature to maximum temperature 230 DEG C; sampling and testing resinous acid value: 5.8mgKOH/g, when 175 DEG C of cone-plates glue for 12.8P, stopped reaction; be cooled to rapidly 90 DEG C of dischargings, obtain target water boiling resistance vibrin.Wherein alkyd feed ratio is 1.2:1.
The water boiling resistance vibrin of above-mentioned preparation, flow agent, other additives, solidifying agent are prepared water boiling resistance coating through high speed dispersion.
(embodiment 3)
In the reactor with agitator, temperature rising reflux device, add 215.9g propylene glycol, 375.9g neopentyl glycol and 412.8g trimethylolethane open and stir and pass into nitrogen, be warming up to 60-80 DEG C and melt as liquid to material.Add 356.2g terephthalic acid, 564.4g m-phthalic acid, 306.6g hexanodioic acid, 256.3gUH-CARB90 (1/1) and 4g tetrabutyl titanate again.Be warming up to water outlet under nitrogen protection, heat up in a steamer a temperature 90-103 DEG C, according to heating up in a steamer a temperature to maximum temperature 225 DEG C; sampling and testing resinous acid value: 3.5mgKOH/g, when 175 DEG C of cone-plates glue for 10.5P, stopped reaction; be cooled to rapidly 90 DEG C of dischargings, obtain target water boiling resistance vibrin.Wherein alkyd feed ratio is 1.3:1.
The water boiling resistance vibrin of above-mentioned preparation, flow agent, other additives, solidifying agent are prepared water boiling resistance coating through high speed dispersion.
(embodiment 4)
In the reactor with agitator, temperature rising reflux device, add 210.9g glycol ether, 410.5g methyl propanediol and 426.3g TriMethylolPropane(TMP) open and stir and pass into nitrogen, be warming up to 60-80 DEG C and melt as liquid to material.Add 456.9g Tetra hydro Phthalic anhydride, 589.1g terephthalic acid, 560.9g hexanodioic acid, 182gUH-CARB50 and 2.9g Dibutyltin oxide again.Be warming up to water outlet under nitrogen protection, heat up in a steamer a temperature 90-103 DEG C, according to heating up in a steamer a temperature to maximum temperature 225 DEG C; sampling and testing resinous acid value: 5.2mgKOH/g, when 175 DEG C of cone-plates glue for 11.8P, stopped reaction; be cooled to rapidly 90 DEG C of dischargings, obtain target water boiling resistance vibrin.
The water boiling resistance vibrin of above-mentioned preparation, flow agent, other additives, solidifying agent are prepared water boiling resistance coating through high speed dispersion.
(embodiment 5)
In the reactor with agitator, temperature rising reflux device, add 170.9g methyl propanediol, 410.2g neopentyl glycol and 460.5g trimethylolethane open and stir and pass into nitrogen, be warming up to 60-80 DEG C and melt as liquid to material.Add 412.5g Tetra hydro Phthalic anhydride, 890.5g m-phthalic acid, 540.1g sebacic acid, 300.9gUH-CARB90 (3/1) and 3.2g titanium isopropylate again.Be warming up to water outlet under nitrogen protection, heat up in a steamer a temperature 90-103 DEG C, according to heating up in a steamer a temperature to maximum temperature 215 DEG C; sampling and testing resinous acid value: 3.2mgKOH/g, when 175 DEG C of cone-plates glue for 12.3P, stopped reaction; be cooled to rapidly 90 DEG C of dischargings, obtain target water boiling resistance vibrin.
The water boiling resistance vibrin of above-mentioned preparation, flow agent, other additives, solidifying agent are prepared water boiling resistance coating through high speed dispersion.
(embodiment 6)
In the reactor with agitator, temperature rising reflux device, add 120.6g ethylene glycol, 256.8g propylene glycol and 548.2g tetramethylolmethane open and stir and pass into nitrogen, be warming up to 60-80 DEG C and melt as liquid to material.Add 894.5g Tetra hydro Phthalic anhydride, 245.9g m-phthalic acid, 500.6g hexanodioic acid, 400.2gUH-CARB90 (1/1) and 3.6g lithium hydroxide again.Be warming up to water outlet under nitrogen protection, heat up in a steamer a temperature 90-103 DEG C, according to heating up in a steamer a temperature to maximum temperature 230 DEG C; sampling and testing resinous acid value: 5.3mgKOH/g, when 175 DEG C of cone-plates glue for 12.6P, stopped reaction; be cooled to rapidly 90 DEG C of dischargings, obtain target water boiling resistance vibrin.
The water boiling resistance vibrin of above-mentioned preparation, flow agent, other additives, solidifying agent are prepared water boiling resistance coating through high speed dispersion.
Made respectively by water boiling resistance vibrin in embodiment 1 ~ 6 and have the water boiling resistance coating that thickness is 300-500 μm, by its physicals of following method evaluation, result is shown in Table 1.
In an embodiment, about the multiple physical properties of described elastic resin, test according to following test method.
1. water boiling resistance:
After 100 DEG C of boiling water boiling 45min, non-foaming, do not ftracture, do not change color as qualified.
2.RCA tests:
With RCA abrasion tester with 175gf, rub 250 times at water boiling resistance coatingsurface, it is qualified for not exposing ground.
3. weather resistance:
Formed and there is the water boiling resistance coating that thickness is 300-500 μm, this film is placed in accelerated aging test instrument (WEL-SUN-DC) after 360 hours, measure RCA Rubbing number by above-mentioned 2nd article of method.After measurement, durability evaluation is as described below: for qualified wherein said value is 70% or higher of the value measured in above-mentioned 2nd article.
Above-described specific embodiment; object of the present invention, technical scheme and beneficial effect are further described; be understood that; the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (8)

1. a water boiling resistance vibrin, is characterized in that: described resin is by by small molecules diprotic acid or acid anhydrides, small molecules dibasic alcohol, organic polyhydric alcohol and polycarbonate diol, carries out polycondensation and obtain under esterifying catalyst exists;
Described esterifying catalyst is the one in tetrabutyl titanate, titanium isopropylate, lithium hydroxide, lead acetate, Dibutyltin oxide or Mono-n-butyltin;
Described small molecules diprotic acid or acid anhydrides are one or more in Tetra hydro Phthalic anhydride, m-phthalic acid, terephthalic acid, hexanodioic acid, sebacic acid;
Described small molecules dibasic alcohol be in methyl propanediol, BDO, 1,6-hexylene glycol, ethylene glycol, glycol ether, propylene glycol or neopentyl glycol one or more;
Described organic polyhydric alcohol be in TriMethylolPropane(TMP), trimethylolethane or tetramethylolmethane one or more.
2. the preparation method of a water boiling resistance vibrin as claimed in claim 1, it is characterized in that: for by small molecules dibasic alcohol, organic polyhydric alcohol adds in the reactor with heat riser and whipping appts, pass into nitrogen, intensification is heated to material and melts as liquid, add small molecules diprotic acid or acid anhydrides successively again, polycarbonate diol and esterifying catalyst, continue under nitrogen protection to be warming up to water outlet, heat up in a steamer a temperature: 90-103 DEG C, temperature of reaction: 140-230 DEG C, reaction is to target acid number: 3-6mgKOH/g, target Cone & Plate viscosity 175 DEG C: 10-13P, stopped reaction, product can be obtained.
3. the preparation method of water boiling resistance vibrin according to claim 2, is characterized in that: described alkyd equivalence ratio is (1.1-1.3): 1 feeds intake.
4. the preparation method of water boiling resistance vibrin according to claim 3, is characterized in that: described alkyd equivalence ratio is that 1.15:1 or 1.2:1 or 1.3:1 feeds intake.
5. the preparation method of water boiling resistance vibrin according to claim 2, is characterized in that: described temperature of reaction is: 215 DEG C.
6. the preparation method of water boiling resistance vibrin according to claim 2, is characterized in that: described temperature of reaction is: 220 DEG C.
7. the preparation method of water boiling resistance vibrin according to claim 2, is characterized in that: described temperature of reaction is: 225 DEG C.
8. the preparation method of water boiling resistance vibrin according to claim 2, is characterized in that: described temperature of reaction is: 230 DEG C.
CN201510566369.3A 2015-09-08 2015-09-08 Water-boiling-resistant polyester resin and preparation method thereof Pending CN105061741A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107400205A (en) * 2017-07-19 2017-11-28 东莞市左镕工实业有限公司 A kind of elastic resin and preparation method thereof
CN113980253A (en) * 2021-10-13 2022-01-28 擎天材料科技有限公司 Bending-resistant easy-extinction polyester resin for low-curing-agent-consumption powder coating and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3207814A (en) * 1961-01-03 1965-09-21 Gen Electric Carbonate-polyester copolymer resinous compositions
CN102241813A (en) * 2010-05-10 2011-11-16 江苏中科金龙化工股份有限公司 Poly (alkene carbonate) diol-polylactic acid segmented copolymer and preparation method thereof
CN102241814A (en) * 2010-05-10 2011-11-16 江苏中科金龙化工股份有限公司 Poly(alkene carbonate)diol-poly(butylene succinate) copolymer and preparation method thereof
US20150018512A1 (en) * 2012-02-06 2015-01-15 Dow Global Technologies Llc Single-pot process for the production of polyester-co-carbonate polyols
CN104725622A (en) * 2013-12-23 2015-06-24 常州华科聚合物股份有限公司 Elastic resin, method for preparing elastic resin and elastic hand feeling paint

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3207814A (en) * 1961-01-03 1965-09-21 Gen Electric Carbonate-polyester copolymer resinous compositions
CN102241813A (en) * 2010-05-10 2011-11-16 江苏中科金龙化工股份有限公司 Poly (alkene carbonate) diol-polylactic acid segmented copolymer and preparation method thereof
CN102241814A (en) * 2010-05-10 2011-11-16 江苏中科金龙化工股份有限公司 Poly(alkene carbonate)diol-poly(butylene succinate) copolymer and preparation method thereof
US20150018512A1 (en) * 2012-02-06 2015-01-15 Dow Global Technologies Llc Single-pot process for the production of polyester-co-carbonate polyols
CN104725622A (en) * 2013-12-23 2015-06-24 常州华科聚合物股份有限公司 Elastic resin, method for preparing elastic resin and elastic hand feeling paint

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107400205A (en) * 2017-07-19 2017-11-28 东莞市左镕工实业有限公司 A kind of elastic resin and preparation method thereof
CN113980253A (en) * 2021-10-13 2022-01-28 擎天材料科技有限公司 Bending-resistant easy-extinction polyester resin for low-curing-agent-consumption powder coating and preparation method thereof
CN113980253B (en) * 2021-10-13 2023-02-03 擎天材料科技有限公司 Bending-resistant easy-extinction polyester resin for low-curing-agent-consumption powder coating and preparation method thereof

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Application publication date: 20151118