CN107573495A - A kind of flexible unsaturated polyester resin - Google Patents
A kind of flexible unsaturated polyester resin Download PDFInfo
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- CN107573495A CN107573495A CN201710849052.XA CN201710849052A CN107573495A CN 107573495 A CN107573495 A CN 107573495A CN 201710849052 A CN201710849052 A CN 201710849052A CN 107573495 A CN107573495 A CN 107573495A
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- polyester resin
- unsaturated polyester
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Abstract
The invention discloses a kind of flexible unsaturated polyester resin, include the raw material of following parts by weight：79~96 parts of unsaturated acids, 64~88 parts of polyether Glycols, 5~10 parts of end carboxyl nitrile rubber, 3~8 parts of phenyl alkylsulf, 12~16 parts of nano-calcium carbonate, 1~3 part of tert-butylhydroquinone, 0.5~2 part of dilauryl thiodipropionate, 0.05~0.15 part of Mono-n-butyltin, 1.3~1.6 parts of methyl ethyl ketone peroxide cobalt iso-octoate system, 0.3~0.6 part of catalyst.Unsaturated polyester resin proposed by the present invention, flexible, hardness is small, it is elongation at break height, strong shock resistance, applied widely, and a kind of preparation method of flexible unsaturated polyester resin is also proposed, the preparation method is simple, gel time is short, and course of reaction is easy to control.
Description
Technical field
The present invention relates to synthetic material technical field, more particularly to a kind of flexible unsaturated polyester resin.
Background technology
A kind of resin that unsaturated polyester resin grows up during being World War II, postwar unsaturated polyester resin
Civil area is rapidly spread to, and spreads to countries in the world.Unsaturated polyester resin has as follows as a kind of thermosetting resin
Advantage：
（1）Price is low, processing performance is good.There is suitable viscosity at room temperature, can at room temperature solidify, be molded under normal pressure,
Solidification process is formed without small molecule, thus easy for construction；
（2）The good combination property of resin, has a wide range of application after solidification.The species of unsaturated polyester resin is more, is made according to different
With requiring, different types of unsaturated polyester resin, such as heat resistant type, flame retardant type, air drying type can be selected.
（3）But there is also the unsaturated polyester resin after some problems, such as solidification for existing unsaturated polyester resin
Hardness it is larger, for usual hardness Barcol 40 or so, elongation at break is low, generally only 5%, and impact resistance is poor, greatly
Limit its application.
The content of the invention
The invention aims to solve shortcoming present in prior art, and a kind of flexible unsaturated polyester (UP) proposed
Resin.
A kind of flexible unsaturated polyester resin, include the raw material of following parts by weight：79~96 parts of unsaturated acids, polyethers binary
64~88 parts of alcohol, 5~10 parts of end carboxyl nitrile rubber, 3~8 parts of phenyl alkylsulf, 12~16 parts of nano-calcium carbonate, tertiary butyl
1~3 part of hydroquinones, 0.5~2 part of dilauryl thiodipropionate, 0.05~0.15 part of Mono-n-butyltin, peroxidating first and second
Ketone -1.3~1.6 parts of cobalt iso-octoate system, 0.3~0.6 part of catalyst.
Preferably, described a kind of flexible unsaturated polyester resin, the raw material of following parts by weight is included：Unsaturated acids 82~
94 parts, 66~84 parts of polyether Glycols, 6~10 parts of end carboxyl nitrile rubber, 4~8 parts of phenyl alkylsulf, nano-calcium carbonate 12
~16 parts, 1~3 part of tert-butylhydroquinone, 0.5~2 part of dilauryl thiodipropionate, Mono-n-butyltin 0.05~0.15
Part, methyl ethyl ketone peroxide -1.3~1.6 parts of cobalt iso-octoate system, 0.4~0.6 part of catalyst.
Preferably, described a kind of flexible unsaturated polyester resin, the raw material of following parts by weight is included：Unsaturated acids 88
Part, 75 parts of polyether Glycols, 8 parts of end carboxyl nitrile rubber, 6 parts of phenyl alkylsulf, 14 parts of nano-calcium carbonate, tertiary butyl is to benzene
2 parts of diphenol, 1.2 parts of dilauryl thiodipropionate, 0.05~0.15 part of Mono-n-butyltin, methyl ethyl ketone peroxide-isooctyl acid
1.4 parts of cobalt system, 0.5 part of catalyst.
Preferably, the unsaturated acids is any one in M-phthalic acid or phthalic acid.
Preferably, the ratio of butadiene and acrylonitrile is 1.2~2.6 in the end carboxyl nitrile rubber：0.5~1.1.
Preferably, the catalyst is maleic anhydride.
The invention also provides a kind of preparation method of flexible unsaturated polyester resin, comprise the following steps：
S1：The unsaturated acids, polyether Glycols and Mono-n-butyltin of corresponding parts by weight are added to the anti-of dropper
Answer in device, and methyl ethyl ketone peroxide-cobalt iso-octoate system is added in dropper, close the company of dropper and reactor
Port valve, heating and the agitating device of reactor are opened, treat that temperature rises to 180~220 DEG C, keep 180~220 DEG C of constant, progress
Esterification；
S2：When the acid number in above-mentioned reactor is down to 22~25mgKOH/g, rise reaction temperature is to 200~240 DEG C, to anti-
The end carboxyl nitrile rubber and catalyst that corresponding parts by weight are added in device are answered, while opens the connection of dropper and reactor
Valve, regulation liquid droping speed are 2ml/min, and side is added dropwise frontier inspection and surveys acid number；
S3：When acid number is 38~44mgKOH/g in reactor, 150~170 DEG C are cooled to, then sequentially add into reactor
Phenyl alkylsulf, nano-calcium carbonate, tert-butylhydroquinone and the dilauryl thiodipropionate of corresponding parts by weight, stirring 10
~30min, is down to room temperature, produces flexible unsaturated polyester resin finished product.
Unsaturated polyester resin proposed by the present invention, flexible, hardness is small, elongation at break height, strong shock resistance, fits
It is wide with scope, and preparation method is simple, gel time is short, and course of reaction is easy to control, and polyester resin is with unsaturated acids and polyethers two
First alcohol is raw material, and esterification is carried out in the presence of Mono-n-butyltin, and poly- by adding the improvement of end carboxyl nitrile rubber
The pliability of ester resin, methyl ethyl ketone peroxide-cobalt iso-octoate system is added dropwise in reactor by dropper, it is anti-to control
The speed answered, adds phenyl alkylsulf after esterification terminates and nano-calcium carbonate changes the rheological characteristic of resin, improves tree
The mouldability of fat, and then improve pliability, extensibility and the anti-wear performance of resin, add tert-butylhydroquinone and thio
Dipropionic acid dilauryl, both, which carry out compounding use, prevents the backbone breaking of unsaturated polyester resin, ensures relative point of resin
Protonatomic mass, avoid carrying out uncontrollable cross-linking reaction in resin between small molecular weight polymer, cause resin is brittle, be hardened,
The phenomenon of intensity decreases occurs.
Embodiment
The present invention is made with reference to specific embodiment further to explain.
Embodiment one
A kind of flexible unsaturated polyester resin proposed by the present invention, include the raw material of following parts by weight：88 parts of M-phthalic acid, gather
73 parts of ether dihydric alcohol, 8 parts of end carboxyl nitrile rubber, 5 parts of phenyl alkylsulf, 14 parts of nano-calcium carbonate, tert-butylhydroquinone 2
Part, 1.2 parts of dilauryl thiodipropionate, 0.1 part of Mono-n-butyltin, methyl ethyl ketone peroxide -1.5 parts of cobalt iso-octoate system,
0.4 part of maleic anhydride.
Its preparation method, comprise the following steps：
S1：The M-phthalic acid, polyether Glycols and Mono-n-butyltin of corresponding parts by weight are added to dropper
In reactor, and methyl ethyl ketone peroxide-cobalt iso-octoate system is added in dropper, closes dropper and reactor
Communicating valve, heating and the agitating device of reactor are opened, treat that temperature rises to 180 DEG C, keep 180 DEG C of constant, progress esterifications；
S2：When the acid number in above-mentioned reactor is down to 22~25mgKOH/g, rise reaction temperature is to 200 DEG C, into reactor
The end carboxyl nitrile rubber and maleic anhydride of corresponding parts by weight are added, while opens the connection of dropper and reactor
Valve, regulation liquid droping speed are 2ml/min, and side is added dropwise frontier inspection and surveys acid number；
S3：When acid number is 38~44mgKOH/g in reactor, 160 DEG C are cooled to, then is sequentially added accordingly into reactor
Phenyl alkylsulf, nano-calcium carbonate, tert-butylhydroquinone and the dilauryl thiodipropionate of parts by weight, 20min is stirred,
Room temperature is down to, produces flexible unsaturated polyester resin finished product.
Embodiment two
A kind of flexible unsaturated polyester resin proposed by the present invention, include the raw material of following parts by weight：96 parts of phthalic acid, gather
88 parts of ether dihydric alcohol, 10 parts of end carboxyl nitrile rubber, 5 parts of phenyl alkylsulf, 16 parts of nano-calcium carbonate, tert-butylhydroquinone
3 parts, 2 parts of dilauryl thiodipropionate, 0.05 part of Mono-n-butyltin, methyl ethyl ketone peroxide -1.6 parts of cobalt iso-octoate system,
0.5 part of maleic anhydride.
Its preparation method, comprise the following steps：
S1：The phthalic acid, polyether Glycols and Mono-n-butyltin of corresponding parts by weight are added to dropper
In reactor, and methyl ethyl ketone peroxide-cobalt iso-octoate system is added in dropper, closes dropper and reactor
Communicating valve, heating and the agitating device of reactor are opened, treat that temperature rises to 220 DEG C, keep 220 DEG C of constant, progress esterifications；
S2：When the acid number in above-mentioned reactor is down to 22~25mgKOH/g, rise reaction temperature is to 240 DEG C, into reactor
The end carboxyl nitrile rubber and maleic anhydride of corresponding parts by weight are added, while opens the connection of dropper and reactor
Valve, regulation liquid droping speed are 2ml/min, and side is added dropwise frontier inspection and surveys acid number；
S3：When acid number is 38~44mgKOH/g in reactor, 170 DEG C are cooled to, then is sequentially added accordingly into reactor
Phenyl alkylsulf, nano-calcium carbonate, tert-butylhydroquinone and the dilauryl thiodipropionate of parts by weight, 30min is stirred,
Room temperature is down to, produces flexible unsaturated polyester resin finished product.
Embodiment three
A kind of flexible unsaturated polyester resin proposed by the present invention, include the raw material of following parts by weight：80 parts of M-phthalic acid, gather
88 parts of ether dihydric alcohol, 10 parts of end carboxyl nitrile rubber, 3 parts of phenyl alkylsulf, 12 parts of nano-calcium carbonate, tert-butylhydroquinone
2 parts, 1 part of dilauryl thiodipropionate, 0.1 part of Mono-n-butyltin, methyl ethyl ketone peroxide -1.3 parts of cobalt iso-octoate system is suitable
0.4 part of anhydride maleique.
Its preparation method, comprise the following steps：
S1：The M-phthalic acid, polyether Glycols and Mono-n-butyltin of corresponding parts by weight are added to dropper
In reactor, and methyl ethyl ketone peroxide-cobalt iso-octoate system is added in dropper, closes dropper and reactor
Communicating valve, heating and the agitating device of reactor are opened, treat that temperature rises to 200 DEG C, keep 200 DEG C of constant, progress esterifications；
S2：When the acid number in above-mentioned reactor is down to 22~25mgKOH/g, rise reaction temperature is to 200~240 DEG C, to anti-
The end carboxyl nitrile rubber and maleic anhydride that corresponding parts by weight are added in device are answered, while opens dropper and reactor
Communicating valve, regulation liquid droping speed are 2ml/min, and side is added dropwise frontier inspection and surveys acid number；
S3：When acid number is 38~44mgKOH/g in reactor, 160 DEG C are cooled to, then is sequentially added accordingly into reactor
Phenyl alkylsulf, nano-calcium carbonate, tert-butylhydroquinone and the dilauryl thiodipropionate of parts by weight, 10min is stirred,
Room temperature is down to, produces flexible unsaturated polyester resin finished product.
Performance detection is carried out to unsaturated polyester resin prepared by embodiment one~tri-, testing result is as follows：
| Embodiment | One | Two | Three |
| Hardness（HB） | 26 | 28 | 25 |
| Elongation at break（%） | 18 | 14 | 16 |
| Gel time（min） | 8 | 10 | 11 |
Testing result shows that the hardness of unsaturated polyester resin prepared by embodiment one~tri- is small, and maximum is only 28HB, and fracture is stretched
Long rate is big, can reach more than 14%, show it is flexible according to formula proposed by the present invention and the resin prepared of preparation method,
It is applied widely, and gel time is short during the course of the reaction, it is only necessary to 8~11min can complete the process of gel,.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.
Claims (7)
1. a kind of flexible unsaturated polyester resin, it is characterised in that include the raw material of following parts by weight：Unsaturated acids 79~96
Part, 64~88 parts of polyether Glycols, 5~10 parts of end carboxyl nitrile rubber, 3~8 parts of phenyl alkylsulf, nano-calcium carbonate 12~
16 parts, 1~3 part of tert-butylhydroquinone, 0.5~2 part of dilauryl thiodipropionate, Mono-n-butyltin 0.05~0.15
Part, methyl ethyl ketone peroxide -1.3~1.6 parts of cobalt iso-octoate system, 0.3~0.6 part of catalyst.
2. a kind of flexible unsaturated polyester resin according to claim 1, it is characterised in that include the original of following parts by weight
Material：82~94 parts of unsaturated acids, 66~84 parts of polyether Glycols, 6~10 parts of end carboxyl nitrile rubber, phenyl alkylsulf 4~8
Part, 12~16 parts of nano-calcium carbonate, 1~3 part of tert-butylhydroquinone, 0.5~2 part of dilauryl thiodipropionate, monobutyl
0.05~0.15 part of tin oxide, methyl ethyl ketone peroxide -1.3~1.6 parts of cobalt iso-octoate system, 0.4~0.6 part of catalyst.
3. a kind of flexible unsaturated polyester resin according to claim 1, it is characterised in that include the original of following parts by weight
Material：88 parts of unsaturated acids, 75 parts of polyether Glycols, 8 parts of end carboxyl nitrile rubber, 6 parts of phenyl alkylsulf, nano-calcium carbonate 14
Part, 2 parts of tert-butylhydroquinone, 1.2 parts of dilauryl thiodipropionate, 0.05~0.15 part of Mono-n-butyltin, peroxidating
MEK -1.4 parts of cobalt iso-octoate system, 0.5 part of catalyst.
4. a kind of flexible unsaturated polyester resin according to claim 1, it is characterised in that the unsaturated acids is isophthalic
Any one in dioctyl phthalate or phthalic acid.
A kind of 5. flexible unsaturated polyester resin according to claim 1, it is characterised in that the end carboxyl nitrile rubber
The ratio of middle butadiene and acrylonitrile is 1.2~2.6：0.5~1.1.
6. a kind of flexible unsaturated polyester resin according to claim 1, it is characterised in that the catalyst is maleic
Dicarboxylic anhydride.
7. a kind of flexible unsaturated polyester resin according to any one of claim 1-6, it is characterised in that it is prepared
Method comprises the following steps：
S1：The unsaturated acids, polyether Glycols and Mono-n-butyltin of corresponding parts by weight are added to the anti-of dropper
Answer in device, and methyl ethyl ketone peroxide-cobalt iso-octoate system is added in dropper, close the company of dropper and reactor
Port valve, heating and the agitating device of reactor are opened, treat that temperature rises to 180~220 DEG C, keep 180~220 DEG C of constant, progress
Esterification；
S2：When the acid number in above-mentioned reactor is down to 22~25mgKOH/g, rise reaction temperature is to 200~240 DEG C, to anti-
The end carboxyl nitrile rubber and catalyst that corresponding parts by weight are added in device are answered, while opens the connection of dropper and reactor
Valve, regulation liquid droping speed are 2ml/min, and side is added dropwise frontier inspection and surveys acid number；
S3：When acid number is 38~44mgKOH/g in reactor, 150~170 DEG C are cooled to, then sequentially add into reactor
Phenyl alkylsulf, nano-calcium carbonate, tert-butylhydroquinone and the dilauryl thiodipropionate of corresponding parts by weight, stirring 10
~30min, is down to room temperature, produces flexible unsaturated polyester resin finished product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710849052.XA CN107573495A (en) | 2017-09-20 | 2017-09-20 | A kind of flexible unsaturated polyester resin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710849052.XA CN107573495A (en) | 2017-09-20 | 2017-09-20 | A kind of flexible unsaturated polyester resin |
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| CN107573495A true CN107573495A (en) | 2018-01-12 |
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| CN105566679A (en) * | 2015-12-29 | 2016-05-11 | 浙江荣泰科技企业有限公司 | Ester compound, and preparation method and application thereof to epoxy resin casting system |
| CN106084705A (en) * | 2016-06-09 | 2016-11-09 | 扬州润友复合材料有限公司 | A kind of high intensity antistatic composite material sheet material and preparation method thereof |
-
2017
- 2017-09-20 CN CN201710849052.XA patent/CN107573495A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070072106A1 (en) * | 2005-09-24 | 2007-03-29 | Samsung Electronics Co., Ltd. | Method of preparing toner using reformed plant oil and toner prepared using the method |
| CN103665311A (en) * | 2013-08-22 | 2014-03-26 | 常州大学 | Modified polyurethane/unsaturated polyester resin dibasic alcohol preparation method |
| CN103724604A (en) * | 2013-12-10 | 2014-04-16 | 浙江天和树脂有限公司 | Preparation method of air-drying unsaturated polyester resin |
| CN104497956A (en) * | 2014-12-18 | 2015-04-08 | 北京天山新材料技术有限公司 | Rapidly-cured double-component polyurethane elastic adhesive and preparation method thereof |
| CN105566679A (en) * | 2015-12-29 | 2016-05-11 | 浙江荣泰科技企业有限公司 | Ester compound, and preparation method and application thereof to epoxy resin casting system |
| CN106084705A (en) * | 2016-06-09 | 2016-11-09 | 扬州润友复合材料有限公司 | A kind of high intensity antistatic composite material sheet material and preparation method thereof |
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Application publication date: 20180112 |