CN109734887A - A kind of high temperature resistance polyester resin and preparation method thereof - Google Patents
A kind of high temperature resistance polyester resin and preparation method thereof Download PDFInfo
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- CN109734887A CN109734887A CN201811644453.2A CN201811644453A CN109734887A CN 109734887 A CN109734887 A CN 109734887A CN 201811644453 A CN201811644453 A CN 201811644453A CN 109734887 A CN109734887 A CN 109734887A
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Abstract
The present invention discloses a kind of high temperature resistance polyester resin, including following raw material: 250-400 parts of polybasic carboxylic acid, 150-250 parts of polyalcohol, and the hydroxyl in raw material and carboxyl molar ratio are controlled as 1.05-1.5:1,0.1-1 parts of catalyst, 0.1-1 parts of antioxidant, 1-10 parts of dimethylbenzene, 30-120 parts of bisphenol-s epoxy resin, 300-600 parts of solvent.The present invention is by introducing sulfuryl on polyester resin strand, because of its special molecular structure property, assign the higher heat resistance of polyester resin and mechanical performance, the common polyester resin glass transition temperature Tg of coatings for tin plate printing is about at 30-50 DEG C at present, softening point is at 80-125 DEG C, and the modified polyester resin of the present invention is all improved in terms of Tg point and softening point, after being configured to coating, it is crosslinked through resolidification, in 160-200 DEG C of tin graphed sheet of baker, no longer soften, so that flower stand print and scald will not be generated.
Description
Technical field
The present invention relates to a kind of high temperature resistance polyester resins and preparation method thereof, belong to coating substrate resin field.
Background technique
Polyester resin causes to make as a major class of coating substrate resin because of the limitation of its heat resistance and mechanical performance
There is certain limitation with range.When synthesizing polyester resin, if introducing some other structures by chemical modification, polyester resin can be made to have
Have the performance that does not have originally, reach improvement and certain prominent performance purpose, to reach special application performance requirement, using compared with
More is epoxy, acrylic acid, silicone modified polyester resin.
As existing Chinese patent " a kind of Heat Resistant Powder Coatings polyester resin and preparation method thereof " (application No. is
201610792940.8), the polyester resin is mainly polymerized by the component of following parts by weight: terminal hydroxy group perfluoropolyether 20-
60 parts, 30-70 parts of polyacid, 10-50 parts of polyalcohol, 1-5 parts of phosphate derivative, 5-15 parts of end-capping reagent, esterification catalyst
0.05-0.3 parts；The polyester resin acid value is 65~75mgKOH/g, and glass transition temperature is 55~65 DEG C, melt viscosity
For 1500~5500mPa.s (200 DEG C), the molar ratio of hydroxyl and carboxyl is 0.80-0.95:1 in raw material.Above-mentioned polyester resin can
With the preferably film-forming under 160-180 DEG C of low temperature, the use cost of perfluoropolyether resin is reduced, the attached of resin is improved
Put forth effort and stability.
Coatings for tin plate printing is a subbranch of coating, and polyester resin is always its main substrate resin, but in application process
In, because its heat resistance is not good enough, cause to be also easy to produce flower stand print and scald in tin graphed sheet coating process.
Summary of the invention
In view of the above existing problems in the prior art, the present invention provides a kind of high temperature resistance polyester resin, with excellent resistance to
High-temperature behavior, adhesive force and patience.The present invention goes back while providing the preparation method of above-mentioned high temperature resistance polyester resin.
To achieve the goals above, a kind of high temperature resistance polyester resin that the present invention uses, by weight, including following original
Material: 250-400 parts of polybasic carboxylic acid, 150-250 parts of polyalcohol, and the hydroxyl in raw material and carboxyl molar ratio are controlled as 1.05-
1.5:1,0.1-1 parts of catalyst, 0.1-1 parts of antioxidant, 1-10 parts of dimethylbenzene, 30-120 parts of bisphenol-s epoxy resin, solvent
300-600 parts.
As an improvement, the polybasic carboxylic acid uses terephthalic acid (TPA), M-phthalic acid, phthalic anhydride, Isosorbide-5-Nitrae-hexamethylene
The arbitrary proportion of one or more of alkane dioctyl phthalate, adipic acid, azelaic acid, sebacic acid, maleic anhydride, trimellitic anhydride is mixed
It closes.
As an improvement, the polyalcohol is ethylene glycol, 1,2-PD, 1,3-PD, methyl propanediol, Isosorbide-5-Nitrae-fourth two
Alcohol, neopentyl glycol, 1,6- hexylene glycol, diethylene glycol, 1,4-CHDM, 2- methyl -2,4- pentanediol, trihydroxy methyl third
The arbitrary proportion of one or more of alkane, pentaerythrite mixes.
As an improvement, the catalyst is in Mono-n-butyltin, Dibutyltin oxide, triphenyltin and Tricyclohexyltin
One or more of arbitrary proportions mixing.
As an improvement, the antioxidant is the mixing of one or both of triphenyl phosphite, tributyl phosphite.
As an improvement, the bisphenol-s epoxy resin is the polymer of bisphenol S and epichlorohydrin reaction, epoxy is worked as
Amount is 300-3000.
As an improvement, the solvent is 150# heavy aromatics, trimethylbenzene, ethylene glycol monobutyl ether, isophorone, butyl glycol ether
The arbitrary proportion of one or more of acetate, diacetone alcohol and dicarboxylic acid esters mixes.
In addition, first weighing each of formula ratio the present invention also provides a kind of preparation method of high temperature resistance polyester resin
Raw material puts into polybasic carboxylic acid, polyalcohol, catalyst in reaction kettle, is to slowly warm up to 220-260 DEG C, reaction 10-15 is small
When, after sample detection acid value, dimethylbenzene is added, is cooled to 140-175 DEG C, adds the bisphenol-s epoxy resin of formula ratio, after
It is continuous to react 1-3 hours, after sample detection qualified, solvent thinning is added to solid content 45-60%, after being uniformly dispersed, filtering
Packaging is finished product.
Compared with prior art, the beneficial effects of the present invention are:
1) present invention, because of its special molecular structure property, is assigned poly- by introducing sulfuryl on polyester resin strand
The higher heat resistance of ester resin and mechanical performance, the common polyester resin glass transition temperature Tg of coatings for tin plate printing about exists at present
30-50 DEG C, softening point is at 80-125 DEG C, and the modified polyester resin of the present invention is all improved in terms of Tg point and softening point,
It after being configured to coating, is crosslinked through resolidification, in 160-200 DEG C of tin graphed sheet of baker, no longer softens, so that flower stand print will not be generated
And scald.
2) epoxy group of the invention by epoxy resin, the ehter bond formed after reaction and epoxy resin self character, are assigned
The superior adhesive force of polyester resin and toughness and better patience are given, can be widely applied to all kinds of coating.
Specific embodiment
In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention is carried out below further detailed
It describes in detail bright.However, it should be understood that the specific embodiments described herein are merely illustrative of the present invention, it is not limited to this hair
Bright range.
Unless otherwise defined, all technical terms and scientific terms used herein are led with technology of the invention is belonged to
The normally understood meaning of the technical staff in domain is identical, and term as used herein in the specification of the present invention is intended merely to retouch
State the purpose of specific embodiment, it is not intended that in the limitation present invention.
A kind of high temperature resistance polyester resin, by weight, including following raw material: 250-400 parts of polybasic carboxylic acid, polyalcohol
150-250 parts, and the hydroxyl in raw material and carboxyl molar ratio are controlled as 1.05-1.5:1；0.1-1 parts of catalyst, antioxidant 0.1-
1 part, 1-10 parts of dimethylbenzene, 30-120 parts of bisphenol-s epoxy resin, 300-600 parts of solvent.
As an improvement, the polybasic carboxylic acid uses terephthalic acid (TPA), M-phthalic acid, phthalic anhydride, Isosorbide-5-Nitrae-hexamethylene
The arbitrary proportion of one or more of alkane dioctyl phthalate, adipic acid, azelaic acid, sebacic acid, maleic anhydride, trimellitic anhydride is mixed
It closes.
As an improvement, the polyalcohol is ethylene glycol, 1,2-PD, 1,3-PD, methyl propanediol, Isosorbide-5-Nitrae-fourth two
Alcohol, neopentyl glycol, 1,6- hexylene glycol, diethylene glycol, 1,4-CHDM, 2- methyl -2,4- pentanediol, trihydroxy methyl third
The arbitrary proportion of one or more of alkane, pentaerythrite mixes.
As an improvement, the catalyst is in Mono-n-butyltin, Dibutyltin oxide, triphenyltin and Tricyclohexyltin
One or more of arbitrary proportions mixing.
As an improvement, the antioxidant is the mixing of one or both of triphenyl phosphite, tributyl phosphite.
As an improvement, the bisphenol-s epoxy resin is the polymer of bisphenol S and epichlorohydrin reaction, epoxy is worked as
Amount is 300-3000.
As an improvement, the solvent is 150# heavy aromatics, trimethylbenzene, ethylene glycol monobutyl ether, isophorone, butyl glycol ether
The arbitrary proportion of one or more of acetate, diacetone alcohol and dicarboxylic acid esters mixes.
In addition, first weighing each of formula ratio the present invention also provides a kind of preparation method of high temperature resistance polyester resin
Raw material puts into polybasic carboxylic acid, polyalcohol, catalyst in reaction kettle, is to slowly warm up to 220-260 DEG C, reaction 10-15 is small
When, after sample detection acid value, dimethylbenzene is added, is cooled to 140-175 DEG C, adds the bisphenol-s epoxy resin of formula ratio, after
It is continuous to react 1-3 hours, after sample detection qualified, solvent thinning is added to solid content 45-60%, after being uniformly dispersed, filtering
Packaging is finished product.
Embodiment 1
A kind of high temperature resistance polyester resin, by weight, including following raw material: polybasic carboxylic acid is 20 parts of adipic acid, isophthalic
320 parts of dioctyl phthalate, 25 parts of trimellitic anhydride；Polyalcohol is 90 parts of methyl propanediol, 50 parts of ethylene glycol, 80 parts of neopentyl glycol；It is anti-
Oxygen agent is 0.5 part of triphenyl phosphite；Catalyst is 0.5 part of Mono-n-butyltin；3 parts of dimethylbenzene；Bisphenol-s epoxy resin
Epoxide equivalent is 450,80 parts；Solvent is 340 parts of 150# heavy aromatics, 38 parts of ethylene glycol monobutyl ether；
The preparation method of the high temperature resistance polyester resin first weighs each raw material of formula ratio, by polybasic carboxylic acid, polyalcohol,
Catalyst and antioxidant are put into reaction kettle, are to slowly warm up to 220 DEG C, are reacted 10 hours, sample detection acid value is lower than
After 25mgKOH/g, dimethylbenzene is added, is cooled to 140 DEG C, adds bisphenol-s epoxy resin, the reaction was continued 2 hours, sampling inspection
After surveying qualified, solvent thinning is added, after being uniformly dispersed, filters and packages as finished product.
Embodiment 2
A kind of high temperature resistance polyester resin, by weight, including following raw material: polybasic carboxylic acid is phthalic anhydride 220
Part, 45 parts of trimellitic anhydride；Polyalcohol is 90 parts of ethylene glycol, 80 parts of neopentyl glycol；Antioxidant is 0.5 part of tributyl phosphite；
Catalyst is 0.5 part of Dibutyltin oxide；6 parts of dimethylbenzene；The epoxide equivalent of bisphenol-s epoxy resin is 1200,120 parts；It is molten
Agent is 380 parts of trimethylbenzene, 60 parts of diacetone alcohol；
The preparation method of the high temperature resistance polyester resin first weighs each raw material of formula ratio, by polybasic carboxylic acid, polyalcohol,
Catalyst and antioxidant are put into reaction kettle, are to slowly warm up to 230 DEG C, are reacted 12 hours, sample detection acid value is less than
After 18mgKOH/g, dimethylbenzene is added, is cooled to 155 DEG C, adds bisphenol-s epoxy resin, the reaction was continued 3 hours, sampling inspection
After surveying qualified, solvent thinning is added, after being uniformly dispersed, filters and packages as finished product.
Embodiment 3
A kind of high temperature resistance polyester resin, by weight, including following raw material: polybasic carboxylic acid be 300 parts of terephthalic acid (TPA),
12 parts of trimellitic anhydride；Polyalcohol is 100 parts of 1,2-PD, 75 parts of neopentyl glycol；Antioxidant is triphenyl phosphite 0.35
Part, 0.25 part of tributyl phosphite；Catalyst is 0.1 part of triphenyltin, 0.3 part of Tricyclohexyltin；4 parts of dimethylbenzene；Bisphenol S type
The epoxide equivalent of epoxy resin is 800,30 parts；Solvent is 280 parts of isophorone, 298 parts of 2-Butoxyethyl acetate；
The preparation method of the high temperature resistance polyester resin first weighs each raw material of formula ratio, by polybasic carboxylic acid, polyalcohol,
Catalyst and antioxidant are put into reaction kettle, are to slowly warm up to 260 DEG C, are reacted 15 hours, sample detection acid value is less than
After 15mgKOH/g, dimethylbenzene is added, is cooled to 175 DEG C, adds bisphenol-s epoxy resin, the reaction was continued 1 hour, sampling inspection
After surveying qualified, solvent thinning is added, after being uniformly dispersed, filters and packages as finished product.
Performance detection is carried out to polyester resin produced by the present invention, concrete outcome is as shown in table 1 below.
The performance of the obtained polyester resin of 1 present invention of table
Analytical table 1 is it is found that polyester resin performance produced by the present invention is met the requirements of the standard.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modification, equivalent replacement or improvement etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (8)
1. a kind of high temperature resistance polyester resin, which is characterized in that by weight, including following raw material: polybasic carboxylic acid 250-400
Part, 150-250 parts of polyalcohol, and the hydroxyl in raw material and carboxyl molar ratio are controlled as 1.05-1.5:1；0.1-1 parts of catalyst,
0.1-1 parts of antioxidant, 1-10 parts of dimethylbenzene, 30-120 parts of bisphenol-s epoxy resin, 300-600 parts of solvent.
2. a kind of high temperature resistance polyester resin according to claim 1, which is characterized in that the polybasic carboxylic acid is used to benzene two
Formic acid, M-phthalic acid, phthalic anhydride, Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic, adipic acid, azelaic acid, sebacic acid, maleic anhydride,
The arbitrary proportion of one or more of trimellitic anhydride mixes.
3. a kind of high temperature resistance polyester resin according to claim 1, which is characterized in that the polyalcohol be ethylene glycol, 1,
2- propylene glycol, 1,3-PD, methyl propanediol, 1,4-butanediol, neopentyl glycol, 1,6- hexylene glycol, diethylene glycol, Isosorbide-5-Nitrae-ring
The arbitrary proportion of one or more of hexane dimethanol, 2- methyl -2,4- pentanediol, trimethylolpropane, pentaerythrite is mixed
It closes.
4. a kind of high temperature resistance polyester resin according to claim 1, which is characterized in that the catalyst is monobutyl oxidation
The arbitrary proportion of one or more of tin, Dibutyltin oxide, triphenyltin and Tricyclohexyltin mixes.
5. a kind of high temperature resistance polyester resin according to claim 1, which is characterized in that the antioxidant is phosphorous triphenyl phosphate
The mixing of one or both of ester, tributyl phosphite.
6. a kind of high temperature resistance polyester resin according to claim 1, which is characterized in that the bisphenol-s epoxy resin is
The polymer of bisphenol S and epichlorohydrin reaction, epoxide equivalent 300-3000.
7. a kind of high temperature resistance polyester resin according to claim 1, which is characterized in that the solvent be 150# heavy aromatics,
One of trimethylbenzene, ethylene glycol monobutyl ether, isophorone, 2-Butoxyethyl acetate, diacetone alcohol and dicarboxylic acid esters are several
The arbitrary proportion mixing of kind.
8. a kind of preparation method of any one of claim 1-7 high temperature resistance polyester resin, which is characterized in that first weigh formula
Each raw material of amount, polybasic carboxylic acid, polyalcohol, catalyst, antioxidant are put into reaction kettle, are to slowly warm up to 220-260 DEG C,
It reacts 10-15 hours, after sample detection acid value, dimethylbenzene is added, is cooled to 140-175 DEG C, adds the bisphenol S type of formula ratio
Epoxy resin, the reaction was continued 1-3 hours, after sample detection qualified, solvent thinning is added to solid content 45-60%, dispersion is equal
After even, filter and package as finished product.
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| CN201811644453.2A CN109734887A (en) | 2018-12-29 | 2018-12-29 | A kind of high temperature resistance polyester resin and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811644453.2A CN109734887A (en) | 2018-12-29 | 2018-12-29 | A kind of high temperature resistance polyester resin and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108302284A (en) * | 2018-02-06 | 2018-07-20 | 中国石油工程建设有限公司华北分公司 | A kind of underground heat-insulated oil pipe and preparation method thereof |
| CN111607075A (en) * | 2020-07-07 | 2020-09-01 | 安徽永利新材料科技有限公司 | High-pressure-resistant poached and acidic-salt-fog-resistant polyester resin for powder and preparation method thereof |
| CN112080000A (en) * | 2020-09-29 | 2020-12-15 | 广州市海珥达环保科技有限公司 | Method for synthesizing poly (p-phthalic acid) -adipic acid-m-epoxy pentadecyl phenol butanediol |
| CN114213644A (en) * | 2021-12-13 | 2022-03-22 | 江苏三木化工股份有限公司 | Saturated polyester resin for reticulate pattern paint and preparation method thereof |
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| CN1970601A (en) * | 2006-12-06 | 2007-05-30 | 上海振华造漆厂 | Epoxy modified polyester resin for paint of coil back surface and its preparation method |
| JP2008241844A (en) * | 2007-03-26 | 2008-10-09 | Dic Corp | Resin composition for toner |
| CN105254846A (en) * | 2015-11-13 | 2016-01-20 | 如皋市金陵化工有限公司 | Synthetic method for bisphenol S epoxy resin |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1970601A (en) * | 2006-12-06 | 2007-05-30 | 上海振华造漆厂 | Epoxy modified polyester resin for paint of coil back surface and its preparation method |
| JP2008241844A (en) * | 2007-03-26 | 2008-10-09 | Dic Corp | Resin composition for toner |
| CN105254846A (en) * | 2015-11-13 | 2016-01-20 | 如皋市金陵化工有限公司 | Synthetic method for bisphenol S epoxy resin |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108302284A (en) * | 2018-02-06 | 2018-07-20 | 中国石油工程建设有限公司华北分公司 | A kind of underground heat-insulated oil pipe and preparation method thereof |
| CN111607075A (en) * | 2020-07-07 | 2020-09-01 | 安徽永利新材料科技有限公司 | High-pressure-resistant poached and acidic-salt-fog-resistant polyester resin for powder and preparation method thereof |
| CN111607075B (en) * | 2020-07-07 | 2022-09-27 | 安徽永利新材料科技有限公司 | High-pressure-resistant poached and acidic-salt-fog-resistant polyester resin for powder and preparation method thereof |
| CN112080000A (en) * | 2020-09-29 | 2020-12-15 | 广州市海珥达环保科技有限公司 | Method for synthesizing poly (p-phthalic acid) -adipic acid-m-epoxy pentadecyl phenol butanediol |
| CN114213644A (en) * | 2021-12-13 | 2022-03-22 | 江苏三木化工股份有限公司 | Saturated polyester resin for reticulate pattern paint and preparation method thereof |
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