CN106380547B - Pre-accelerated type unsaturated polyester resin of anti-gel time drift and preparation method thereof - Google Patents
Pre-accelerated type unsaturated polyester resin of anti-gel time drift and preparation method thereof Download PDFInfo
- Publication number
- CN106380547B CN106380547B CN201610868589.6A CN201610868589A CN106380547B CN 106380547 B CN106380547 B CN 106380547B CN 201610868589 A CN201610868589 A CN 201610868589A CN 106380547 B CN106380547 B CN 106380547B
- Authority
- CN
- China
- Prior art keywords
- unsaturated polyester
- polyester resin
- gel time
- time drift
- type unsaturated
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The present invention relates to pre-accelerated type unsaturated polyester resins of a kind of anti-gel time drift and preparation method thereof, and appropriate gel time drift inhibitor is added in the unsaturated polyester resin that promotor is added and mixes；Wherein promotor is cobalt class compound；Gel time drift inhibitor is the polyhydroxy-alcohol containing at least two hydroxyls.When the anti-gel time drift of the invention pre-accelerated type unsaturated polyester resin resting period is longer, can to avoid or mitigate the drift phenomenon of pre-accelerated type unsaturated polyester resin gel time.
Description
Technical field
The present invention relates to the preparation and application of a kind of unsaturated polyester resin and the unsaturated polyester resin, belong to
In organic high molecular compound preparation technical field.
Background technique
Unsaturated polyester resin is most common one kind in thermosetting resin, it is by monounsaturated dicarboxylic acid, unsaturated binary
Line polymer made of acid and dihydric alcohol polycondensation, the resin solution with certain viscosity to be formed is diluted by cross-linking monomer,
Abbreviation UPR.Excellent processing performance is unsaturated polyester resin biggest advantage, becomes a kind of compound if with glass fiber reinforcement
Material is commonly called as glass reinforced plastic.It has many excellent performances such as high light weight, intensity, resistant to chemical etching, electrical isolation, saturating microwave.No
The concern of saturated polyester resin and its composite material by industry, after World War II, is rapidly spread to civil field,
Have become the indispensable important materials of the development of the national economy.
The gel of unsaturated polyester resin and solidification are that the addition polymerization of long chain type unsaturated polyester (UP) molecule and unsaturated monomer is anti-
It answers, initiator is needed to cause, start reaction, be then swift in response and carry through to the end.In the case where initiator is used alone, though
Can so unsaturated polyester resin be made to solidify, but solidification process is often difficult to control, this problem needs to solve using promotor
Certainly.The effect of promotor is so that stable initiator is become unstable by redox reaction, so that at normal temperature can be fast
Speed is decomposed to cause cross-linking process.Initiator and promotor not directly mix absolutely, otherwise can cause vigorous reaction, so that explosion
Kindling.Often add promotor in advance in unsaturated polyester resin manufacturing process, that is, claims pre-accelerated type unsaturated polyester resin, insatiable hunger
It can be used with the pre-accelerated type of polyester resin dangerous caused by family is exempted because of promotor improper use or mixed with initiator.
In order to meet requirement of the user to composite material, need to adjust the gel time of naval stores, but with unsaturation
Slowly varying, referred to as " gel time drift can occur to extend or shorten for the increase of polyester resin period of storage, gel time
Move ", so that making unsaturated polyester resin when in use becomes not meeting the requirement using process conditions.Pre-accelerated type unsaturation is poly-
Ester resin provides great convenience to client, but unsaturated polyester resin of the gel time in storage than not promoting often have it is larger
Drift.The reason is that complicated chemical reaction can occur in unsaturated polyester resin within storage period.
Summary of the invention
The technical problem to be solved by the present invention is to provide a kind of it is possible to prevente effectively from or the pre-accelerated type unsaturated polyester (UP) of mitigation
The pre-accelerated type unsaturated polyester resin of the anti-gel time drift of resin gel time drift phenomenon and its preparation method.
A kind of technical solution that the present invention proposes to solve above-mentioned technical problem is: a kind of anti-gel time drift is pre-accelerated
When gel is added in the preparation method of type unsaturated polyester resin in the pre-accelerated type unsaturated polyester resin that promotor has been added
Between drift about and inhibitor and mix；The promotor is cobalt class compound；The gel time drift inhibitor is containing at least two
The polyhydroxy-alcohol of a hydroxyl.
The gel time drift inhibitor is one of ethylene glycol, propylene glycol, glycerine, 1,3-BDO or more
Kind.
The additional amount of the promotor accounts for the pre-accelerated type unsaturated polyester resin gross mass of the anti-gel time drift
0.1%~0.3%；It is poly- that the additional amount of the gel time drift inhibitor accounts for the pre-accelerated type unsaturation of the anti-gel time drift
The 0.5%~1.5% of ester resin gross mass.
The cobalt naphthenate solution that the promotor is the cobalt iso-octoate solution that cobalt content is 12% or cobalt content is 6%.
The unsaturated polyester resin is obtained after reactant to be warming up to 180 DEG C~210 DEG C progress polycondensation dehydrations
Polymer be cooled to 140 DEG C~160 DEG C, polymerization inhibitor and styrene is then added and dilutes to obtain unsaturated polyester resin, inhibits
The dosage of agent accounts for the unsaturated polyester resin gross mass 50ppm~700ppm, and the dosage of styrene accounts for the unsaturated polyester (UP)
The unsaturated polyester resin is cooled to 40 DEG C or less addition promotors and obtains pre-accelerated type not by resin gross mass 40%~60%
Saturated polyester resin.
The reactant includes dihydric alcohol and unsaturated dibasic acid or acid anhydrides, and the hydroxyl of reactant and the molar ratio of carboxyl are
1.05: 1~1.2: 1；The dihydric alcohol be one of ethylene glycol, propylene glycol, diglycol and dipropylene glycol or
It is a variety of；The unsaturated dibasic acid or acid anhydrides are one or both of maleic anhydride, fumaric acid.
The reactant further includes monounsaturated dicarboxylic acid or acid anhydrides, the monounsaturated dicarboxylic acid or acid anhydrides be phthalic anhydride,
One of M-phthalic acid and terephthalic acid (TPA) are a variety of.
The polymerization inhibitor is one of hydroquinone, methyl hydroquinone, p-tert-Butylcatechol or a variety of.
When adding gel time drift inhibitor into the pre-accelerated type unsaturated polyester resin, first not by pre-accelerated type
Saturated polyester resin is kept the temperature to 35 DEG C~45 DEG C.
The another technical solution that the present invention proposes to solve above-mentioned technical problem is: a kind of anti-gel time drift promotees in advance
Into type unsaturated polyester resin, including account for the pre-accelerated type unsaturated polyester resin gross mass of the anti-gel time drift 0.1%~
0.3% promotor and account for the solidifying of the pre-accelerated type unsaturated polyester resin gross mass 0.5%~1.5% of the anti-gel time drift
Glue time drift inhibitor；The promotor is cobalt class compound；The gel time drift inhibitor is containing at least two
The polyhydroxy-alcohol of hydroxyl.
The gel time drift inhibitor is one of ethylene glycol, propylene glycol, glycerine, 1,3-BDO or more
Kind, the cobalt naphthenate solution that the promotor is the cobalt iso-octoate solution that cobalt content is 12% or cobalt content is 6%.
The present invention has the effect of positive: the pre-accelerated type unsaturated polyester resin of anti-gel time drift of the invention is added
The polyhydroxy-alcohol for containing at least two hydroxyls drifts about inhibitor as gel time, can to avoid or mitigate pre-accelerated type insatiable hunger
With the drift phenomenon of polyester resin gel time.The preferred propylene glycol of gel time drift inhibitor, glycerine, ethylene glycol and 1,3-
Butanediol, wherein gel time drift about inhibitory effect: propylene glycol > glycerine > ethylene glycol > 1,3-BDO.Of the invention is anti-
The gel time pre-accelerated type unsaturated polyester resin that drifts about will not influence the stability and craftsmanship of resin, ensure that the matter of resin
It measures reliable and stable.
Specific embodiment
Embodiment 1
The pre-accelerated type unsaturated polyester resin of the anti-gel time drift of the present embodiment, in the preparation, first to equipped with nitrogen
Protection, thermometer, is fractionated in four mouthfuls of containers of column device blender, puts into propylene glycol 192.85g, ethylene glycol 43.03g, adjacent benzene
Dicarboxylic acid anhydride 290.84g, maleic anhydride 96.20g, are warming up to 210 DEG C of progress polycondensation reactions, and reaction to acid value is 16~22
MgKOH/g obtains polymer.
Polymer is cooled to 140 DEG C again, styrene 430.66g, methyl hydroquinone are put into four mouthfuls of containers
0.070g, hydroquinone 0.080g are sufficiently stirred 1 hour, are uniformly mixed it.
Being cooled to 40 DEG C or less investment cobalt contents is 12% cobalt iso-octoate solution 1.20g, when then keeping the temperature to 35 DEG C~45 DEG C
Gel time drift inhibitor glycerine 1.98g, ethylene glycol 3.05g are put into, is sufficiently stirred 1 hour, obtains after mixing
The pre-accelerated type unsaturated polyester resin of anti-gel time drift.
Embodiment 2
The pre-accelerated type unsaturated polyester resin of the anti-gel time drift of the present embodiment, in the preparation, first to equipped with nitrogen
Protection, thermometer, is fractionated in four mouthfuls of containers of column device blender, puts into propylene glycol 115.58g, diglycol
143.30g, M-phthalic acid 217.80g, are warming up to 210 DEG C of progress polycondensation reactions, when reaction is to solid acid value < 2mgKOH/g,
Maleic anhydride 128.48g is put into again, is warming up to 205 DEG C of progress polycondensation reactions, reaction to acid value is 12~18 mgKOH/g,
Obtain polymer.
Polymer is cooled to 140 DEG C again, styrene 465.58g, hydroquinone 0.082g are put into four mouthfuls of containers,
P-tert-Butylcatechol 0.378g is sufficiently stirred 1 hour, is uniformly mixed it.
Being cooled to 40 DEG C or less investment cobalt contents is 6% cobalt naphthenate solution 3.00g, when then keeping the temperature to 35 DEG C~45 DEG C
Gel time drift inhibitor propylene glycol 10.17g is put into, is sufficiently stirred 1 hour, obtains the drift of anti-gel time after mixing
Move pre-accelerated type unsaturated polyester resin.
Embodiment 3
The pre-accelerated type unsaturated polyester resin of the anti-gel time drift of the present embodiment, in the preparation, first to equipped with nitrogen
Protection, thermometer, is fractionated in four mouthfuls of containers of column device blender, puts into propylene glycol 149.26g, diglycol
31.62g, terephthalic acid (TPA) 182.84g, Dibutyltin oxide 0.182g are warming up to 210 DEG C of progress polycondensation reactions, and reaction is to admittedly
When body acid value < 2mgKOH/g, then propylene glycol 94.68g is put into, maleic anhydride 215.69g is warming up to 205 DEG C and contracts
Poly- reaction, reaction to acid value are 6~12mgKOH/g, obtain polymer.
Polymer is cooled to 140 DEG C again, styrene 404.5g, methyl hydroquinone are put into four mouthfuls of containers
0.040g, p-tert-Butylcatechol 0.640g are sufficiently stirred 1 hour, are uniformly mixed it.
Being cooled to 40 DEG C or less investment cobalt contents is 12% cobalt iso-octoate solution 2.00g, when then keeping the temperature to 35 DEG C~45 DEG C
Gel time drift inhibitor 1,3-BDO 15.0g is put into, is sufficiently stirred 1 hour, when obtaining anti-gel after mixing
Between drift about pre-accelerated type unsaturated polyester resin.
Comparative example 1
The pre-accelerated type unsaturated polyester resin of the anti-gel time drift of this comparative example, in the preparation, first to equipped with nitrogen
Protection, thermometer, is fractionated in four mouthfuls of containers of column device blender, puts into propylene glycol 192.85g, ethylene glycol 43.03g, adjacent benzene
Dicarboxylic acid anhydride 290.84g, maleic anhydride 96.20g, are warming up to 210 DEG C of progress polycondensation reactions, and reaction to acid value is 16~22
MgKOH/g obtains polymer.
Polymer is cooled to 140 DEG C again, styrene 430.66g, methyl hydroquinone are put into four mouthfuls of containers
0.070g, hydroquinone 0.080g are sufficiently stirred 1 hour, are uniformly mixed it.
Being cooled to 40 DEG C or less investment cobalt contents is 12% cobalt iso-octoate solution 1.20g, is sufficiently stirred 1 hour, is uniformly mixed
Pre-accelerated type unsaturated polyester resin is obtained afterwards.
Comparative example 2
The pre-accelerated type unsaturated polyester resin of the anti-gel time drift of the present embodiment, in the preparation, first to equipped with nitrogen
Protection, thermometer, is fractionated in four mouthfuls of containers of column device blender, puts into propylene glycol 115.58g, diglycol
143.30g, M-phthalic acid 217.80g, are warming up to 210 DEG C of progress polycondensation reactions, when reaction is to solid acid value < 2mgKOH/g,
Maleic anhydride 128.48g is put into again, is warming up to 205 DEG C of progress polycondensation reactions, reaction to acid value is 12~18 mgKOH/g,
Obtain polymer.
Polymer is cooled to 140 DEG C again, styrene 465.58g, hydroquinone 0.082g are put into four mouthfuls of containers,
P-tert-Butylcatechol 0.378g is sufficiently stirred 1 hour, is uniformly mixed it.
Being cooled to 40 DEG C or less investment cobalt contents is 6% cobalt naphthenate solution 3.00g, is sufficiently stirred 1 hour, is uniformly mixed
Pre-accelerated type unsaturated polyester resin is obtained afterwards.
Comparative example 3
The pre-accelerated type unsaturated polyester resin of the anti-gel time drift of the present embodiment, in the preparation, first to equipped with nitrogen
Protection, thermometer, is fractionated in four mouthfuls of containers of column device blender, puts into propylene glycol 149.26g, diglycol
31.62g, terephthalic acid (TPA) 182.84g, Dibutyltin oxide 0.182g are warming up to 210 DEG C of progress polycondensation reactions, and reaction is to admittedly
When body acid value < 2mgKOH/g, then propylene glycol 94.68g is put into, maleic anhydride 215.69g is warming up to 205 DEG C and contracts
Poly- reaction, reaction to acid value are 6~12mgKOH/g, obtain polymer.
Polymer is cooled to 140 DEG C again, styrene 404.5g, methyl hydroquinone are put into four mouthfuls of containers
0.040g, p-tert-Butylcatechol 0.640g are sufficiently stirred 1 hour, are uniformly mixed it.
Being cooled to 40 DEG C or less investment cobalt contents is 12% cobalt iso-octoate solution 2.00g, is sufficiently stirred 1 hour, is uniformly mixed
Pre-accelerated type unsaturated polyester resin is obtained afterwards.
Comparative test
Gel time drift test is carried out to the unsaturated polyester resin of each embodiment and each comparative example respectively.
Gel time drift test be on day 1, the 5th day, the 30th day, the 60th day respectively according to GB/T 7193-2008
In " unsaturated polyester resin test method " 4.6 shown in method, under conditions of 25 DEG C of water-bath, in glass be added test
Sample 100g constant temperature, adding initiator methyl ethyl ketone peroxide, (Tianjin Akzo Nobel's peroxide Co., Ltd produces
Butanox M-50) 1.5g, measure 25 DEG C of gel times of unsaturated polyester resin.5th day, the 30th day, 25 DEG C of the 60th day
Gel time calculates change rate i.e. drift rate on the basis of the 1st day 25 DEG C of gel times respectively, the results are shown in Table 1.
1 gel time of table drift test result
As shown in table 1, even if the pre-accelerated type unsaturated polyester resin storage 60 of the anti-gel time drift of embodiment 1 to 3
It, the variation of 25 DEG C of gel times is limited, drift rate at most just 20% or so.And the pre-accelerated type unsaturation of comparative example 1 to 3 is poly-
Ester resin, due to there is no to add gel time inhibitor, so 25 DEG C of gel times are extended by about one time at storage 30 days,
The use of resin can be seriously affected.
Obviously, the above embodiment is merely an example for clearly illustrating the present invention, and is not to of the invention
The restriction of embodiment.For those of ordinary skill in the art, it can also be made on the basis of the above description
Its various forms of variation or variation.There is no necessity and possibility to exhaust all the enbodiments.And these belong to this hair
The obvious changes or variations that bright spirit is extended out are still in the protection scope of this invention.
Claims (9)
1. a kind of preparation method of the pre-accelerated type unsaturated polyester resin of anti-gel time drift, it is characterised in that: be added
Appropriate gel time drift inhibitor is added in the pre-accelerated type unsaturated polyester resin of promotor and mixes；The promotor is
Cobalt class compound；The gel time drift inhibitor is glycerine.
2. the preparation method of the pre-accelerated type unsaturated polyester resin of anti-gel time drift according to claim 1, feature
Be: the additional amount of the promotor accounts for the 0.1% of the pre-accelerated type unsaturated polyester resin gross mass of the anti-gel time drift
~0.3%；The additional amount of the gel time drift inhibitor accounts for the pre-accelerated type unsaturated polyester (UP) tree of the anti-gel time drift
The 0.5%~1.5% of rouge gross mass.
3. the preparation method of the pre-accelerated type unsaturated polyester resin of anti-gel time drift according to claim 2, feature
It is: the cobalt naphthenate solution that the promotor is the cobalt iso-octoate solution that cobalt content is 12% or cobalt content is 6%.
4. the preparation of the pre-accelerated type unsaturated polyester resin of anti-gel time drift according to any one of claims 1 to 3
Method, it is characterised in that: unsaturated polyester resin is that reactant is warming up to 180 DEG C~210 DEG C progress polycondensation dehydrations, is obtained
To polymer be cooled to 140 DEG C~160 DEG C, be then added what polymerization inhibitor and styrene diluted, the dosage of polymerization inhibitor accounts for
The unsaturated polyester resin gross mass 50ppm~700ppm, the dosage of styrene account for the unsaturated polyester resin gross mass
40%~60%, the unsaturated polyester resin is cooled to 40 DEG C or less addition promotors and obtains pre-accelerated type unsaturated polyester (UP) tree
Rouge.
5. the preparation method of the pre-accelerated type unsaturated polyester resin of anti-gel time drift according to claim 4, feature
Be: the reactant includes dihydric alcohol and unsaturated dibasic acid or acid anhydrides, and the hydroxyl of reactant and the molar ratio of carboxyl are
1.05: 1~1.2: 1；The dihydric alcohol be one of ethylene glycol, propylene glycol, diglycol and dipropylene glycol or
It is a variety of；The unsaturated dibasic acid or acid anhydrides are one or both of maleic anhydride, fumaric acid.
6. the preparation method of the pre-accelerated type unsaturated polyester resin of anti-gel time drift according to claim 5, feature
Be: the reactant further includes monounsaturated dicarboxylic acid or acid anhydrides, and the monounsaturated dicarboxylic acid or acid anhydrides are phthalic anhydride, isophthalic
One of dioctyl phthalate and terephthalic acid (TPA) are a variety of；The polymerization inhibitor is hydroquinone, methyl hydroquinone, to tert-butyl o
One of benzenediol is a variety of.
7. the preparation of the pre-accelerated type unsaturated polyester resin of anti-gel time drift according to any one of claims 1 to 3
Method, it is characterised in that:, first will be pre- when adding gel time drift inhibitor into the pre-accelerated type unsaturated polyester resin
Promoted type unsaturated polyester resin is kept the temperature to 35 DEG C~45 DEG C.
8. a kind of pre-accelerated type unsaturated polyester resin of anti-gel time drift, which is characterized in that when including accounting for the anti-gel
Between drift about pre-accelerated type unsaturated polyester resin gross mass 0.1%~0.3% promotor and to account for the anti-gel time drift pre-
0.5%~1.5% gel time drift inhibitor of promoted type unsaturated polyester resin gross mass；The promotor is cobalt class
Close object；The gel time drift inhibitor is glycerine.
9. the pre-accelerated type unsaturated polyester resin of anti-gel time drift according to claim 8, it is characterised in that: the rush
It is the cobalt iso-octoate solution that cobalt content is 12% or the cobalt naphthenate solution that cobalt content is 6% into agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610868589.6A CN106380547B (en) | 2016-09-30 | 2016-09-30 | Pre-accelerated type unsaturated polyester resin of anti-gel time drift and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610868589.6A CN106380547B (en) | 2016-09-30 | 2016-09-30 | Pre-accelerated type unsaturated polyester resin of anti-gel time drift and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106380547A CN106380547A (en) | 2017-02-08 |
| CN106380547B true CN106380547B (en) | 2018-12-07 |
Family
ID=57936205
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610868589.6A Active CN106380547B (en) | 2016-09-30 | 2016-09-30 | Pre-accelerated type unsaturated polyester resin of anti-gel time drift and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106380547B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1281891A (en) * | 1968-09-28 | 1972-07-19 | Bp Chemical Internat Ltd | Polyester stabilisers |
| CN101835834A (en) * | 2007-10-25 | 2010-09-15 | 帝斯曼知识产权资产管理有限公司 | Unsaturated polyester resin compositions |
| CN103834254A (en) * | 2013-12-17 | 2014-06-04 | 常州华日新材有限公司 | Bi-component coating unsaturated polyester resin and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS447135Y1 (en) * | 1965-11-27 | 1969-03-18 |
-
2016
- 2016-09-30 CN CN201610868589.6A patent/CN106380547B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1281891A (en) * | 1968-09-28 | 1972-07-19 | Bp Chemical Internat Ltd | Polyester stabilisers |
| CN101835834A (en) * | 2007-10-25 | 2010-09-15 | 帝斯曼知识产权资产管理有限公司 | Unsaturated polyester resin compositions |
| CN103834254A (en) * | 2013-12-17 | 2014-06-04 | 常州华日新材有限公司 | Bi-component coating unsaturated polyester resin and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106380547A (en) | 2017-02-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101633729B (en) | Method for preparing unsaturated polyster resin by industrial dicyclopentadiene | |
| CN102911371B (en) | Hyperbranched polyester modified acrylic resin and preparation method thereof | |
| Meiorin et al. | Polymeric networks based on tung oil: Reaction and modification with green oil monomers | |
| Chen et al. | New bio-based polymeric thermosets synthesized by ring-opening polymerization of epoxidized soybean oil with a green curing agent | |
| US9546126B2 (en) | Natural based branched compositions | |
| CN101735405B (en) | Imitation marble unsaturated polyester resin and preparation method thereof | |
| Aung et al. | A comparative study of acrylate oligomer on Jatropha and Palm oil-based UV-curable surface coating | |
| CN105482085A (en) | Anti-ultraviolet copolyester and preparation method thereof | |
| CN105602220B (en) | SMC material and preparation method thereof | |
| Arvin et al. | High performance bio-based thermosets from dimethacrylated epoxidized sucrose soyate (DMESS) | |
| CN106380547B (en) | Pre-accelerated type unsaturated polyester resin of anti-gel time drift and preparation method thereof | |
| CN103834254B (en) | Double-component coat unsaturated polyester resin and preparation using method thereof | |
| CN102086253A (en) | Acrylic acid modified sulfonate-based water-reducible alkyd resins | |
| Kolot et al. | Vernonia oil–based acrylate and methacrylate polymers and interpenetrating polymer networks with epoxy resins | |
| CN104693429A (en) | Short oil alkyd resin and preparation method thereof | |
| CN105482087A (en) | Anti-yellowing unsaturated polyester resin and synthetic method thereof | |
| Mustafa et al. | Synthesis and characterization of novel alkyds derived from palm oil based polyester resin | |
| Arvin et al. | Effect of nature and extent of functional group modification on properties of thermosets from methacrylated epoxidized sucrose soyate | |
| Setien et al. | Comparison of epoxidation methods for biobased oils: dioxirane intermediates generated from Oxone versus peracid derived from hydrogen peroxide | |
| CN112778464A (en) | Styrene-free unsaturated polyester resin and preparation method and application thereof | |
| CN107955113A (en) | A kind of flexible unsaturated polyester resin of no styrene and preparation method thereof | |
| CN106748765B (en) | A kind of UV curable polyester and the preparation method and application thereof | |
| CZ298291B6 (en) | Impregnation, pouring, coating composition and use thereof | |
| CN106589335B (en) | A kind of polyarylate Photoactivatable coating composition and polyarylate protective coating prepared therefrom | |
| Ho et al. | Enhancement of UV resistance and thermal stability of the unsaturated polyester material by introducing MHHPA fragment into the molecular skeleton |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |