CN109705279A - A kind of glycerin modification unsaturated polyester resin and preparation method thereof - Google Patents
A kind of glycerin modification unsaturated polyester resin and preparation method thereof Download PDFInfo
- Publication number
- CN109705279A CN109705279A CN201811587597.9A CN201811587597A CN109705279A CN 109705279 A CN109705279 A CN 109705279A CN 201811587597 A CN201811587597 A CN 201811587597A CN 109705279 A CN109705279 A CN 109705279A
- Authority
- CN
- China
- Prior art keywords
- unsaturated polyester
- polyester resin
- glycerin modification
- predetermined temperature
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention discloses a kind of glycerin modification unsaturated polyester resins, include the following raw material, the content of each raw material indicates by mass percentage are as follows: glycerol 4-10%, monoacid 6-12%, catalyst 0.02-0.05%, dihydric alcohol 3-9%, polymerization inhibitor 0.02-0.05%, crosslinking agent 25-40%, cis-butenedioic anhydride 10-20%, dicyclopentadiene 8-18%, binary acid 4-10%.The glycerin modification unsaturated polyester resin is applied in daylighting tile preparation, can make the daylighting tile of preparation that there is preferable toughness, higher mechanical property, refractive index are closer with glass fiber reinforced materials, and product surface air-drying property is good.
Description
Technical field
The present invention relates to a kind of daylighting tile polyester resin, and in particular to a kind of applied to production glass reinforced plastic mechanism daylighting tile
Glycerin modification unsaturated polyester resin and preparation method thereof.
Background technique
Unsaturated polyester resin is usually as made of dihydric alcohol and binary acid polycondensation with ester bond and unsaturated double-bond
Linear polymeric polymer, then different types of unsaturated polyester resin is formed after styrene monomer thinning.Unsaturated polyester (UP)
Resin possesses good workability, widely used, in vehicular traffic, building, shipbuilding, chemical industry equipment, electronic apparatus, sport device
The industries such as material and articles for daily use have application, occupy an important position in composite industry.
Daylighting tile is a kind of high property that the preparation of continuously shaped pultrude process is used by unsaturated polyester resin and glass fibre
Can composite material, have good translucency, higher heat resistance, thermal expansion coefficient it is small, will not be because of caused by cold and hot contraction
The advantages that roof leaking；It can be applied to steel-structure factory building, gymnasium, public place and room temperature etc..
Continuously shaped pultrude process, which refers to, is uniformly coated with the fiber glass reinforcement for being soaked with unsaturated polyester resin
Between double-layer films, sandwich is formed, is squeezed through compression roller, is allowed to closely knit, excludes bubble；After thickness as defined in reaching,
It is examined through gel solidification demoulding, cutting, cleaning, finally obtains product, forming process, which is carried out continuously, substantially increases production efficiency.
Chinese patent ZL201310190280.2 discloses a kind of preparation method of glycerin modification unsaturated polyester resin, should
Reaction method includes polycondensation and cross-linking reaction, it is characterised in that organic tin catalyst is added in polycondensation reaction.This method early period
Glycerol and other dihydric alcohols, binary acid, monoacid mixing copolyreaction are held during the reaction since glycerol is trihydroxylic alcohol
Reaction easily is crosslinked, viscosity increased dramatically, and there are risks for process control.
Chinese patent application 201710103067.1 discloses a kind of preparation method of glycerin modification unsaturated polyester (UP), the hair
Bright middle using diethylene glycol (DEG), gained resin cured matter is with the advantages that good toughness, heat release is slow, and thermostabilization is good；Prepared by this method
Unsaturated polyester resin flexibility it is good, but intensity and heat distortion temperature are relatively low, be applied in terms of strong lighting watt by
To limitation, and early period is reacted by glycerol and other dihydric alcohols, binary acid, monoacid mixing copolyreaction, control process is same
In the presence of crosslinking risk.
Therefore, existing public technology for glycerin modification unsaturated polyester (UP) preparation method, there are preparation process risk is big,
The shortcomings that being unfavorable for the normal use of industrialized production.
Summary of the invention
Present invention seek to address that problem as described above.The present invention provides a kind of glycerin modification unsaturated polyester resin and
Preparation method during the preparation process first blocks glycerol with monoacid, is allowed to become binary alcohol intermediate, then again with
Cis-butenedioic anhydride, binary acid reaction, to reduce the crosslinking risk in reaction process；Dicyclopentadiene is introduced simultaneously, so that resin has
Good air-drying property and intensity.
According to an aspect of the present invention, the present invention provides a kind of glycerin modification unsaturated polyester resins, comprising as follows
The content of raw material, each raw material is expressed as follows by mass percentage:
Wherein, the content of each raw material is expressed as follows by mass percentage:
Wherein, the monoacid is one of benzoic acid, glacial acetic acid, formic acid and propionic acid or a variety of；
The binary acid is one of phthalic anhydride, M-phthalic acid, maleic anhydride or a variety of.
Wherein, the dihydric alcohol is one of ethylene glycol, diethylene glycol (DEG), propylene glycol, dipropylene glycol and neopentyl glycol
Or it is a variety of.
Wherein,
The catalyst is one of dibutyl tin, tetraethyl titanate, stannous octoate and Mono-n-butyltin or a variety of；
The polymerization inhibitor be hydroquinone, adjacent methyl hydroquinone, p-tert-Butylcatechol, tert-butyl hydroquinone,
One of 1,4-benzoquinone and 2,6- di-t-butyl -4- cresols are a variety of；
The crosslinking agent is in styrene, methyl methacrylate, α-methylstyrene and triallyl cyanurate
It is one or more.
Glycerin modification unsaturated polyester resin of the invention, the monoacid of glycerol, 6-12% in raw material comprising 4-10%
And the catalyst of 0.02-0.05%.Preferably, glycerol 6-10%, monoacid 8-12%.The carboxyl and glycerol of monoacid
A hydroxy esterification reaction, to block to glycerol, two functional group's alcohol are become by the alcohol of trifunctional.It is sweet by controlling
Oily dosage can control the extent of reaction of end capping reaction, thus during the reaction as far as possible consume trifunctional glycerol completely,
It avoids generating cross-linking reaction, reduces preparation risk.
Wherein, monoacid is one of benzoic acid, glacial acetic acid, formic acid and propionic acid or a variety of；Binary acid is O-phthalic
One of acid anhydrides, M-phthalic acid, maleic anhydride are a variety of；Catalyst is dibutyl tin, tetraethyl titanate, octanoic acid Asia
One of tin and Mono-n-butyltin are a variety of.
Glycerin modification unsaturated polyester resin of the invention further includes the dihydric alcohol of 3-9%, the cis-butenedioic anhydride of 10-20%, water 2-
5%, the binary acid of the dicyclopentadiene of 8-18% and 4-10%, it is preferred that dihydric alcohol 5-9%, cis-butenedioic anhydride 15-20%, water
2.5-4%, dicyclopentadiene 10-16%, binary acid 6-10%.Wherein, dihydric alcohol is ethylene glycol, diethylene glycol (DEG), propylene glycol, a contracting
One of dipropylene glycol and neopentyl glycol are a variety of.It meanwhile further including the friendship of the polymerization inhibitor and 25-40% of 0.02-0.05%
Join agent, it is preferred that polymerization inhibitor 0.02-0.05%, crosslinking agent 30-40%.Wherein, polymerization inhibitor is hydroquinone, adjacent methyl
One of hydroquinone, p-tert-Butylcatechol, tert-butyl hydroquinone, 1,4-benzoquinone and 2,6- di-t-butyl -4- cresols
Or it is a variety of；Crosslinking agent be one of styrene, methyl methacrylate, α-methylstyrene and triallyl cyanurate or
It is a variety of.On the one hand level of inhibitor considers storage stability, on the one hand consider that client uses technique, uses technique need according to client
Seek the different usage amounts of selection.
According to another aspect of the present invention, the preparation method of aforementioned glycerin modification unsaturated polyester resin is provided, including
Following steps:
1S: crosslinking dilution agent:
It will be dissolved in water that crosslinking agent is measured at its 2-5 times, it is spare after agitation and dilution；
2S: end capping reaction:
Under inert gas shielding, glycerol, monoacid, catalyst are successively put into the first reaction flask, open stirring；Heating
It is warming up to 165-175 DEG C of progress insulation reaction 1-2h；It is continuously heating to 205-210 DEG C, wait react to acid value 11 hereinafter, being cooled to
120-140 DEG C, product is obtained, it is spare；
During the preparation process, monoacid is first reacted with glycerol, the alcohol of glycerol trifunctional can be made to become two officials
Alcohol can be rolled into a ball, avoids generating cross-linking reaction, reduces preparation risk.
3S: cis-butenedioic anhydride is reacted with dicyclopentadiene:
Under inert gas shielding, cis-butenedioic anhydride, water are successively put into the second reaction flask, are opened stirring, are warming up to 120-130 DEG C
Keep the temperature 0.5-1h；Then dicyclopentadiene is added dropwise, flows back 2-3 hours after dripping off；
Then the product for putting into dihydric alcohol, binary acid, the polymerization inhibitor of 1/4-1/3 formula ratio and step 2S, is warming up to
205-210 DEG C the reaction was continued, subsequent vacuum dehydration, until acid value reaches 38-40, after viscosity reaches 180-200mPas, obtains anti-
Object is answered, it is spare；
Cis-butenedioic anhydride and water generate maleic acid under heating conditions, and there are two double bond, chemical property in dicyclopentadiene
It is very active, addition occurs under heating conditions with maleic acid, generates half ester structure, then proceedes to and binary acid and two
Esterification occurs for first alcohol.
During the reaction, acid value size determines the molecular size range of product, has an impact to the mechanical property of product.Through
Multiple experimental test is crossed, acid value, which is controlled, can reach corrugated plating performance requirement in 38-40.The above viscosity index is single using crosslinking
Body styrene is adjusted and is obtained, and control more meets the use technique of client in this viscosity range.
4S: the reactant in step 3S cross-linking reaction: is cooled to 120-130 DEG C hereinafter, putting into remaining polymerization inhibitor, stirring
After uniformly, the diluted crosslinking agent of step 1S is added, stirs evenly to get glycerin modification unsaturated polyester resin.
Wherein, it to be nitrogen that the inert gas that is passed through is reacted in step 2S and 3S, can also be substituted for argon gas etc. other
Inert gas.
Compared with prior art, synthesis technology of the invention is simple, and product is good with the transparency, intensity is high, good toughness, gas
The advantages that stemness is good；And cost advantage is obvious.Glycerin modification unsaturated polyester resin prepared by the present invention is applied to daylighting
Watt preparation on, can make preparation daylighting tile have preferable toughness, higher mechanical property, refractive index, with fiberglass reinforced material
Expect closer, and product surface air-drying property is good.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with of the invention specific
Technical solution of the present invention is clearly and completely described in embodiment, it is clear that described embodiment is the present invention one
Divide embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making
Every other embodiment obtained, shall fall within the protection scope of the present invention under the premise of creative work.It should be noted that
In the case where not conflicting, the features in the embodiments and the embodiments of the present application can mutual any combination.
Glycerin modification unsaturated polyester resin of the invention includes the following raw material, and the content of each raw material is by mass percentage
It indicates are as follows: glycerol 4-10%, monoacid 6-12%, catalyst 0.02-0.05%, dihydric alcohol 3-9%, polymerization inhibitor 0.02-
0.05%, crosslinking agent 25-40%, cis-butenedioic anhydride 10-20%, water 2-5%, dicyclopentadiene 8-18%, binary acid 4-10%.
Preferably, the content of each raw material indicates by mass percentage are as follows: glycerol 6-10%, monoacid 8-12%, catalyst
0.02-0.05%, dihydric alcohol 5-9%, polymerization inhibitor 0.02-0.05%, crosslinking agent 30-40%, cis-butenedioic anhydride 15-20%, water 2.5-
4%, dicyclopentadiene 10-16%, binary acid 6-10%.
Wherein, monoacid is one of benzoic acid, glacial acetic acid, formic acid and propionic acid or a variety of；
Binary acid is one of phthalic anhydride, M-phthalic acid, maleic anhydride or a variety of；
Dihydric alcohol is one of ethylene glycol, diethylene glycol (DEG), propylene glycol, dipropylene glycol and neopentyl glycol or a variety of；
Catalyst is one of dibutyl tin, tetraethyl titanate, stannous octoate and Mono-n-butyltin or a variety of；
Polymerization inhibitor be hydroquinone, adjacent methyl hydroquinone, p-tert-Butylcatechol, tert-butyl hydroquinone, to benzene
One of quinone and 2,6- di-t-butyl -4- cresols are a variety of；
Crosslinking agent is one of styrene, methyl methacrylate, α-methylstyrene and triallyl cyanurate
Or it is a variety of.
The preparation method of the glycerin modification unsaturated polyester resin, includes the following steps:
1S: crosslinking dilution agent:
It will be dissolved in water that crosslinking agent is measured at its 2-5 times, it is spare after agitation and dilution；
2S: end capping reaction:
Under inert gas shielding, glycerol, monoacid, catalyst are successively put into the first reaction flask, open stirring；Heating
It is warming up to 165-175 DEG C of progress insulation reaction 1-2h；It is continuously heating to 205-210 DEG C, wait react to acid value 11 hereinafter, being cooled to
120-140 DEG C, product is obtained, it is spare；
3S: cis-butenedioic anhydride is reacted with dicyclopentadiene:
Under inert gas shielding, cis-butenedioic anhydride, water are successively put into the second reaction flask, are opened stirring, are warming up to 120-130 DEG C
Keep the temperature 0.5-1h；Then dicyclopentadiene is added dropwise, during dropwise addition, temperature is maintained at 125 DEG C, flows back 2-3 hours after dripping off；
Then the product for putting into dihydric alcohol, binary acid, the polymerization inhibitor of 1/4-1/3 formula ratio and step 2S, is warming up to
205-210 DEG C the reaction was continued, subsequent vacuum dehydration, until acid value reaches 38-40, after viscosity reaches 180-200mPas, obtains anti-
Object is answered, it is spare；
4S: the reactant in step 3S cross-linking reaction: is cooled to 120-130 DEG C hereinafter, putting into remaining polymerization inhibitor, stirring
After uniformly, the diluted crosslinking agent of step 1S is added, stirs evenly to get glycerin modification unsaturated polyester resin.
The some embodiments of the application glycerin modification unsaturated polyester resin are listed below.
Embodiment
Table 1 shows the specific embodiment of each material content in partial glycerol modified unsaturated polyester resin, each raw material pair
The numerical value answered is mass percent/%.
Wherein, monoacid selects benzoic acid, and production firm is Jiangsu Shun Feng Chemical Co., Ltd..
Catalyst selects Mono-n-butyltin, and production firm is Hangzhou Yu Hao Chemical Industry Science Co., Ltd；
Dihydric alcohol selects the combination of diethylene glycol (DEG) (dihydric alcohol 1) or diethylene glycol (DEG) and propylene glycol (dihydric alcohol 2), and wherein diethylene glycol (DEG) is raw
Production manufacturer is Yanshan Petrochemical, and propylene glycol production firm is Yanshan Petrochemical；
Polymerization inhibitor selects hydroquinone；
Crosslinking agent selects the combination of styrene (crosslinking agent 1) or styrene and methyl methacrylate (crosslinking agent 2).
Binary acid selects phthalic anhydride.
It should be pointed out that specific type selected by the above raw material is not to other the specific kind of choosings of the application component
It selects and is construed as limiting.
1 glycerin modification unsaturated polyester resin specific embodiment list of table
| Raw material | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Glycerol | 8.3 | 6.5 | 8.3 | 6.5 | 7.4 | 7.4 |
| Monoacid | 10.7 | 8.5 | 10.7 | 8.5 | 9.6 | 9.6 |
| Catalyst | 0.03 | 0.04 | 0.03 | 0.04 | 0.03 | 0.02 |
| Cis-butenedioic anhydride | 19.1 | 15.02 | 19.1 | 15.02 | 15.06 | 15.06 |
| Water | 3.6 | 2.8 | 3.6 | 2.8 | 3.2 | 3.2 |
| Dicyclopentadiene | 11.0 | 15.2 | 11.0 | 14.2 | 13.1 | 13.1 |
| Dihydric alcohol 1 | 8.2 | 6.5 | 0 | 0 | 3.7 | 3.7 |
| Dihydric alcohol 2 | 0 | 0 | 5.88 | 5.66 | 2.6 | 2.6 |
| Binary acid | 6.2 | 8.1 | 6.2 | 8.1 | 7.15 | 7.15 |
| Polymerization inhibitor | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 |
| Crosslinking agent 1 | 32.85 | 32.32 | 35.177 | 34.16 | 38.14 | 33.14 |
| Crosslinking agent 2 | 0 | 5 | 0 | 5 | 0 | 5 |
Test case
Beneficial effect in order to further illustrate the present invention compares survey to the performance of each embodiment and comparative example
Examination.
Comparative example 1:
On the basis of embodiment 3, other raw materials are constant, and the cis-butenedioic anhydride amount removing dicyclopentadiene and accordingly consuming obtains sweet
Oily modified unsaturated polyester resin.
Comparative example 2:
On the basis of embodiment 3, other raw materials are constant, remove the amount of unitary acid blocked glycerol and corresponding consumption cis-butenedioic anhydride, obtain
To bicyclic modified unsaturated polyester resin.
The modified unsaturated resin of embodiment 1-6 and comparative example 1-2 are applied on daylighting tile, respectively to properties into
Row test.It is specific as shown in table 2.
2 performance comparison test result of table
It can be seen that glycerin modification unsaturated-resin polyester of the invention applied to daylighting tile from the above contrast test data
On have preferable toughness, higher mechanical property, refractive index is closer with glass fiber reinforced materials, and product surface air-drying property is good
It is good.
To sum up, glycerin modification unsaturated polyester resin of the present invention, synthesis technology is simple, and product has the transparency
Well, the advantages that intensity height, good toughness, good air-drying property, and cost advantage is obvious.
Descriptions above can combine implementation individually or in various ways, and these variants all exist
Within protection scope of the present invention.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations.Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (10)
1. a kind of glycerin modification unsaturated polyester resin, which is characterized in that include the following raw material, the content of each raw material presses matter
Amount percentage is expressed as follows:
2. glycerin modification unsaturated polyester resin as described in claim 1, which is characterized in that the content of each raw material presses matter
Amount percentage is expressed as follows:
3. glycerin modification unsaturated polyester resin as claimed in claim 1 or 2, which is characterized in that the monoacid is benzene first
One of acid, glacial acetic acid, formic acid and propionic acid are a variety of；
The binary acid is one of phthalic anhydride, M-phthalic acid, maleic anhydride or a variety of.
4. glycerin modification unsaturated polyester resin as claimed in claim 1 or 2, which is characterized in that the dihydric alcohol is second two
One of alcohol, diethylene glycol (DEG), propylene glycol, dipropylene glycol and neopentyl glycol are a variety of.
5. glycerin modification unsaturated polyester resin as claimed in claim 1 or 2, which is characterized in that
The catalyst is one of dibutyl tin, tetraethyl titanate, stannous octoate and Mono-n-butyltin or a variety of；
The polymerization inhibitor be hydroquinone, adjacent methyl hydroquinone, p-tert-Butylcatechol, tert-butyl hydroquinone, to benzene
One of quinone and 2,6- di-t-butyl -4- cresols are a variety of；
The crosslinking agent is one of styrene, methyl methacrylate, α-methylstyrene and triallyl cyanurate
Or it is a variety of.
6. a kind of preparation method of glycerin modification unsaturated polyester resin as described in any one in claim 1-5, feature exist
In including the following steps:
1S: crosslinking dilution agent:
It will be dissolved in water that crosslinking agent is measured at its 2-5 times, it is spare after agitation and dilution；
2S: end capping reaction:
Under inert gas shielding, glycerol, monoacid, catalyst are successively put into the first reaction flask, open stirring；Heat temperature raising
Insulation reaction 1-2h is carried out to the first predetermined temperature；It is continuously heating to the second predetermined temperature, wait react to acid value 11 hereinafter, cooling down
To third predetermined temperature, product is obtained, it is spare；
3S: cis-butenedioic anhydride is reacted with dicyclopentadiene:
Under inert gas shielding, cis-butenedioic anhydride, water are successively put into the second reaction flask, are opened stirring, are warming up to the 4th predetermined temperature
Carry out heat preservation 0.5-1h；Then dicyclopentadiene is added dropwise, flows back 2-3 hours after dripping off；
Then the product for putting into dihydric alcohol, binary acid, the polymerization inhibitor of 1/4-1/3 formula ratio and the step 2S is warming up to the
The reaction was continued for five predetermined temperatures, subsequent vacuum dehydration, until reactant is obtained after acid value, viscosity touch the mark, it is spare；
4S: cross-linking reaction: being cooled to the 6th predetermined temperature for the reactant in the step 3S hereinafter, put into remaining polymerization inhibitor,
After mixing evenly, the diluted crosslinking agent of step 1S is added, stirs evenly to get the glycerin modification unsaturated polyester resin.
7. the preparation method of glycerin modification unsaturated polyester resin as claimed in claim 6, which is characterized in that the step 2S
In, first predetermined temperature is 165-175 DEG C, and second predetermined temperature is 205-210 DEG C, and the third predetermined temperature is
120-140℃。
8. the preparation method of glycerin modification unsaturated polyester resin as claimed in claim 6, which is characterized in that the step 3S
In, the 4th predetermined temperature is 120-130 DEG C, and the 5th predetermined temperature is 205-210 DEG C.
9. the preparation method of glycerin modification unsaturated polyester resin as claimed in claim 6, which is characterized in that the step 3S
In, the index of the acid value is 38-40, and the index of the viscosity is 180-200mPas.
10. the preparation method of glycerin modification unsaturated polyester resin as claimed in claim 6, which is characterized in that the step
In 4S, the 6th predetermined temperature is 120-130 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811587597.9A CN109705279A (en) | 2018-12-25 | 2018-12-25 | A kind of glycerin modification unsaturated polyester resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811587597.9A CN109705279A (en) | 2018-12-25 | 2018-12-25 | A kind of glycerin modification unsaturated polyester resin and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109705279A true CN109705279A (en) | 2019-05-03 |
Family
ID=66257479
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811587597.9A Pending CN109705279A (en) | 2018-12-25 | 2018-12-25 | A kind of glycerin modification unsaturated polyester resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109705279A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111825835A (en) * | 2020-07-22 | 2020-10-27 | 肖宏品 | Water-based polyester resin and preparation method thereof |
| CN114213797A (en) * | 2022-01-11 | 2022-03-22 | 陈小云 | Wear-resistant scratch-resistant SMC (sheet molding compound) molding compound and preparation method thereof |
| CN115181220A (en) * | 2022-09-13 | 2022-10-14 | 山东旺林新材料有限公司 | Preparation method and application of p-benzene type unsaturated polyester resin |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212173A (en) * | 2011-05-04 | 2011-10-12 | 肇庆福田化学工业有限公司 | Method for synthesizing unsaturated polyester resin for artificial marble |
| CN102219882A (en) * | 2011-05-04 | 2011-10-19 | 肇庆福田化学工业有限公司 | Method for synthesizing unsaturated polyester resin by utilizing glycerol |
| CN102443114A (en) * | 2010-10-13 | 2012-05-09 | 常州华科树脂有限公司 | Air-dried unsaturated polyester resin with excellent comprehensive property and its preparation method |
| CN103193966A (en) * | 2013-04-27 | 2013-07-10 | 肇庆福田化学工业有限公司 | Unsaturated polyester resin for artificial stone and synthesis method thereof |
| CN103951793A (en) * | 2014-04-15 | 2014-07-30 | 吴桥昊通树脂有限公司 | Method for producing unsaturated polyester resin by using glycerinum |
| CN104163891A (en) * | 2014-05-29 | 2014-11-26 | 上海展辰涂料有限公司 | Unsaturated resin modified by two air-drying monomers |
| CN105669907A (en) * | 2016-01-13 | 2016-06-15 | 淄博鲁凯树脂有限公司 | Low-contraction unsaturated polyester resin used for pultrusion and preparation method thereof |
| CN108219122A (en) * | 2018-01-26 | 2018-06-29 | 山东宏信化工股份有限公司 | The preparation method of daylighting tile resin |
-
2018
- 2018-12-25 CN CN201811587597.9A patent/CN109705279A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102443114A (en) * | 2010-10-13 | 2012-05-09 | 常州华科树脂有限公司 | Air-dried unsaturated polyester resin with excellent comprehensive property and its preparation method |
| CN102212173A (en) * | 2011-05-04 | 2011-10-12 | 肇庆福田化学工业有限公司 | Method for synthesizing unsaturated polyester resin for artificial marble |
| CN102219882A (en) * | 2011-05-04 | 2011-10-19 | 肇庆福田化学工业有限公司 | Method for synthesizing unsaturated polyester resin by utilizing glycerol |
| CN103193966A (en) * | 2013-04-27 | 2013-07-10 | 肇庆福田化学工业有限公司 | Unsaturated polyester resin for artificial stone and synthesis method thereof |
| CN103951793A (en) * | 2014-04-15 | 2014-07-30 | 吴桥昊通树脂有限公司 | Method for producing unsaturated polyester resin by using glycerinum |
| CN104163891A (en) * | 2014-05-29 | 2014-11-26 | 上海展辰涂料有限公司 | Unsaturated resin modified by two air-drying monomers |
| CN105669907A (en) * | 2016-01-13 | 2016-06-15 | 淄博鲁凯树脂有限公司 | Low-contraction unsaturated polyester resin used for pultrusion and preparation method thereof |
| CN108219122A (en) * | 2018-01-26 | 2018-06-29 | 山东宏信化工股份有限公司 | The preparation method of daylighting tile resin |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111825835A (en) * | 2020-07-22 | 2020-10-27 | 肖宏品 | Water-based polyester resin and preparation method thereof |
| CN114213797A (en) * | 2022-01-11 | 2022-03-22 | 陈小云 | Wear-resistant scratch-resistant SMC (sheet molding compound) molding compound and preparation method thereof |
| CN115181220A (en) * | 2022-09-13 | 2022-10-14 | 山东旺林新材料有限公司 | Preparation method and application of p-benzene type unsaturated polyester resin |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109705279A (en) | A kind of glycerin modification unsaturated polyester resin and preparation method thereof | |
| CN1213091C (en) | Unsaturated polyester resins | |
| WO2015090150A1 (en) | Photo-curable insulating varnish, preparation method therefor and application method thereof | |
| TWI490645B (en) | Photosensitive resin composition, photosensitive resin varnish, photosensitive resin film, and photosensitive resin hardenable compositon | |
| JP7024923B1 (en) | Polyester, film and adhesive compositions, as well as adhesive sheets, laminates and printed wiring boards | |
| TW200911862A (en) | (Meth)acrylate compound, resin composition containing the same, cured product of the resin composition, and energy ray-curable resin composition for optical lens sheet and cured product thereof | |
| JP2015520793A (en) | Polyester primer composition, optical film using the same, and polarizing plate including the same | |
| JP6981581B1 (en) | Adhesive compositions, as well as adhesive sheets, laminates and printed wiring boards | |
| CN107267079B (en) | Polyester film | |
| JP2016535876A (en) | Optical film including primer layer containing polyester resin and polarizing plate using the same | |
| KR20180003460A (en) | Polyester muti-layer film | |
| JP2012007154A (en) | Polyester resin, process for producing polyester resin and aqueous liquid of polyester resin | |
| JP7405298B2 (en) | Polyester, film and adhesive compositions, as well as adhesive sheets, laminates and printed wiring boards | |
| JPH09241496A (en) | Unsaturated polyester resin composition and sheet-like molding material | |
| WO2019062428A1 (en) | Polyester segmented copolymer and preparation method therefor and application thereof | |
| TW201631334A (en) | Light control panel and optical imaging device | |
| KR101685499B1 (en) | Unsaturated polyester resin having high elongation and rigidity modulus and the method of manufacturing the same | |
| CN110437730A (en) | A kind of light weather-proof optical grade PET cured film | |
| JP7136312B2 (en) | polyesters, adhesives and films | |
| MXPA06014368A (en) | Impregnating resin formulation. | |
| CN113637146B (en) | Tung oil acid maleic anhydride modified vinyl ester resin and preparation method and application thereof | |
| CN101713910B (en) | Method of producing multilayer coating film | |
| CN114133869A (en) | Graphene-modified ultraviolet-curing insulating paint and preparation method thereof | |
| JP2019157091A (en) | Active energy ray-curable resin composition, and coating agent and sheet using the same | |
| JPS58225112A (en) | Unsaturated polyester resin composition and laminated sheet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190503 |
|
| RJ01 | Rejection of invention patent application after publication |