CN106496532A - A kind of extra-weather-proof polyester resin for powder coating - Google Patents
A kind of extra-weather-proof polyester resin for powder coating Download PDFInfo
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- CN106496532A CN106496532A CN201611141447.6A CN201611141447A CN106496532A CN 106496532 A CN106496532 A CN 106496532A CN 201611141447 A CN201611141447 A CN 201611141447A CN 106496532 A CN106496532 A CN 106496532A
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- antioxidant
- acid
- alcohol
- polyester resin
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- 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
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
-
- 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
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention belongs to organic high molecular compound technical field, specifically refer to a kind of extra-weather-proof polyester resin for powder coating, raw material includes alcohol, acid, catalyst, antioxidant and accelerator, the mol ratio of wherein alcohol/acid is 1.05 1.2, alcohol includes that neopentyl glycol and trimethylolpropane, trimethylolpropane account for the 1wt% 7wt% of alcohol gross mass；Acid includes one or two in M-phthalic acid and 1,4 cyclohexane cyclohexanedimethanodibasics；Antioxidant accounts for the 0.17wt% 0.75wt% of acid, alcohol gross mass, including one or more in antioxidant 3114, antioxidant 1076 and irgasfos 168.The raw material weatherability of the present invention is fine, and yellowing-resistant, the sterically hindered vitrification point that can improve greatly resin and price is suitable, and with suitable molecular weight of polyesters size and suitable viscosity, avoid crosslinking excessively make coating become fragile and to impact unfavorable, the different antioxidant of mechanism of action produces cooperative effect, and the antioxidant effect of reinforced resin, aberration are stable, persistency is good, is effectively improved durability of coating.
Description
Technical field
The invention belongs to organic high molecular compound technical field, specifically refers to a kind of extra-weather-proof polyester tree used for powder coating
Fat.
Background technology
Powdery paints is a kind of solid powdery coating of non-volatile solvent, with solvent-free, low stain, stock utilization
High, the low advantage of energy expenditure, is widely used in household electrical appliance, plant equipment, anti-corrosion pipeline and building material technical field.Powder
Last coating crosslinks reaction using resin after heating with firming agent, form insoluble hard coat, and when temperature is high, the coating is only
Can decompose, without softening as thermoplastic resin coating, thus with stronger mechanical performance.
Polyester resin powder coating compared with other types powdery paints, with unique property, for example, due to polyester tree
Fat carries polar group, so powder utilization is higher than epoxy resin, is difficult yellowing in baking process, and glossiness is high, good leveling property, paint
Film is plentiful, of light color etc..Polyester powder coating is used in a large number because of its excellent combination property, weather resistance and relatively low cost
In outdoor facilities such as building, automobile, traffic routes, at present the thermosetting powder coating of more than half be all using polyester resin as
Prepared by base material.
With the expansion of application, the weather resistance of polyester powder coating also exposes its wretched insufficiency, and determines
The key of polyester powder coating weatherability is still matrix resin.Therefore, it is necessary to develop super-weathering resistance polyester tree used for powder coating
Fat.
Content of the invention
The technical problem to be solved in the present invention is to provide a kind of super-weathering resistance polyester resin for powder coating, with superpower
Weatherability.
The present invention is achieved in that a kind of extra-weather-proof polyester resin for powder coating, the raw material bag of the polyester resin
Include alcohol, acid, catalyst, antioxidant and accelerator, the mol ratio of wherein described alcohol/acid is 1.05-1.2, the alcohol includes new penta
Glycol and trimethylolpropane, the trimethylolpropane account for the 1wt%-7wt% of alcohol gross mass；
The acid includes one or two in M-phthalic acid and 1,4 cyclohexanedicarboxylic acid；
The antioxidant accounts for acid, the 0.17wt%-0.75wt% of alcohol gross mass, including antioxidant 3114, antioxidant 1076 and antioxygen
One or more in agent 168；
The catalyst is Mono-n-butyltin, and the accelerator is ammonium salt or microcosmic salt.
Used as a kind of improvement, the mol ratio of the alcohol/acid is 1.1.
Used as a kind of improvement, the trimethylolpropane accounts for the 5wt% of alcohol gross mass.
Used as a kind of improvement, the acid includes M-phthalic acid and Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic, the M-phthalic acid and
The mol ratio of 1,4 cyclohexanedicarboxylic acid is（1-3）:（1-3）.
Used as further improving, the mol ratio of the M-phthalic acid and Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic is 1:1.
Used as a kind of improvement, the antioxidant accounts for the 0.5wt% of acid alcohol gross mass.
Used as a kind of improvement, the antioxidant includes antioxidant 3114 and irgasfos 168, the antioxidant 3114 and antioxygen
The mass ratio of agent 168 is（1-2）:（1-2）.
Used as further improving, the antioxidant 3114 is 2 with the mass ratio of irgasfos 168:1.
Used as a kind of improvement, the antioxidant includes antioxidant 1076 and irgasfos 168, the antioxidant 3114 and antioxygen
The mass ratio of agent 168 is（1-2）:（1-2）.
The present invention is fed using two-step method, produces polyester resin by melt-polycondensation pyroreaction, and product is without dirt
Dye, is processed less, cost-effective.
In the raw material of the present invention, neopentyl glycol is a kind of weatherability glycol monomer well, and yellowing-resistant, space bit
The vitrification point and price that resistance can improve greatly resin is suitable, and M-phthalic acid and Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic have good
Weatherability and yellowing resistance energy, reactivity ratio are higher to this dioctyl phthalate, tree light-protection rate height is obtained, determines through lot of experiments and closes
Suitable acid-alcohol ratio, to obtain suitable molecular weight of polyesters size and suitable viscosity, determines suitable trimethylolpropane consumption, makes
The Tg of polyester is raised, and is improved resin resistance to water, is improved and smear mechanical performance, improve the storage stability of powder, while avoiding using
Amount excessive, make resin synthesis process gel, also avoid crosslinking excessively make coating become fragile and to impact unfavorable, mechanism of action is different
Antioxidant produces cooperative effect, and the antioxidant effect of reinforced resin, aberration are stable, and persistency is good, is effectively improved durability of coating.
Specific embodiment
In order that technological means, creation characteristic, reached purpose and effect that the present invention is realized are easy to understand, tie below
Specific embodiment is closed, the present invention is expanded on further.
Embodiment 1
A kind of extra-weather-proof polyester resin for powder coating, its raw material include alcohol, acid, catalyst, antioxidant and accelerator, wherein
The mol ratio of alcohol/acid is 1.05, and alcohol includes that neopentyl glycol and trimethylolpropane, trimethylolpropane account for alcohol gross mass
1wt%；
Acid includes two kinds in M-phthalic acid and 1,4 cyclohexanedicarboxylic acid；
Antioxidant accounts for acid, the 0.17wt% of alcohol gross mass, including antioxidant 3114 and irgasfos 168；
Catalyst is Mono-n-butyltin, and accelerator is ammonium salt or microcosmic salt.
In the present embodiment, the mol ratio of M-phthalic acid and Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic is 1:3, antioxidant 3114 and antioxygen
The mass ratio of agent 168 is 1:2.
Embodiment 2
A kind of extra-weather-proof polyester resin for powder coating, the raw material of polyester resin include alcohol, acid, catalyst, antioxidant and promotion
Agent, the wherein mol ratio of alcohol/acid are 1.1, and alcohol includes that neopentyl glycol and trimethylolpropane, trimethylolpropane account for alcohol gross mass
5wt%；
Acid includes M-phthalic acid and 1,4 cyclohexanedicarboxylic acid；
Antioxidant accounts for acid, the 0.5wt% of alcohol gross mass, including antioxidant 3114 and irgasfos 168；
Catalyst is Mono-n-butyltin, and the accelerator is ammonium salt or microcosmic salt.
In the present embodiment, the mol ratio of M-phthalic acid and Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic is 1:1, antioxidant 3114 and antioxygen
The mass ratio of agent 168 is 2:1.
Embodiment 3
A kind of extra-weather-proof polyester resin for powder coating, the raw material of polyester resin include alcohol, acid, catalyst, antioxidant and promotion
Agent, the wherein mol ratio of alcohol/acid are 1.1, and alcohol includes that neopentyl glycol and trimethylolpropane, trimethylolpropane account for alcohol gross mass
5wt%；
Acid includes M-phthalic acid and 1,4 cyclohexanedicarboxylic acid；
Antioxidant accounts for acid, the 0.5wt% of alcohol gross mass, including antioxidant 3114 and irgasfos 168；
Catalyst is Mono-n-butyltin, and accelerator is ammonium salt or microcosmic salt.
In the present embodiment, the mol ratio of M-phthalic acid and Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic is 1:1, antioxidant 3114 and antioxygen
The mass ratio of agent 168 is 1:1.
Embodiment 4
A kind of extra-weather-proof polyester resin for powder coating, the raw material of polyester resin include alcohol, acid, catalyst, antioxidant and promotion
Agent, the mol ratio of wherein described alcohol/acid is 1.2, and alcohol includes neopentyl glycol and trimethylolpropane, and it is total that trimethylolpropane accounts for alcohol
The 7wt% of quality；
Acid includes M-phthalic acid and 1,4 cyclohexanedicarboxylic acid；
Antioxidant accounts for acid, the 0.75wt% of alcohol gross mass, including antioxidant 1076 and irgasfos 168；
Catalyst is Mono-n-butyltin, and accelerator is ammonium salt or microcosmic salt.
In the present embodiment, the mol ratio of M-phthalic acid and Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic is 2:1, antioxidant 3114 and antioxygen
The mass ratio of agent 168 is 1:1.
Embodiment 5
A kind of extra-weather-proof polyester resin for powder coating, the raw material of polyester resin include alcohol, acid, catalyst, antioxidant and promotion
Agent, the mol ratio of wherein described alcohol/acid is 1.2, and alcohol includes neopentyl glycol and trimethylolpropane, and it is total that trimethylolpropane accounts for alcohol
The 7wt% of quality；
Acid includes M-phthalic acid and 1,4 cyclohexanedicarboxylic acid；
Antioxidant accounts for acid, the 0.75wt% of alcohol gross mass, including antioxidant 1076 and irgasfos 168；
Catalyst is Mono-n-butyltin, and accelerator is ammonium salt or microcosmic salt.
In the present embodiment, the mol ratio of M-phthalic acid and Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic is 2:1, antioxidant 3114 and antioxygen
The mass ratio of agent 168 is 3:1.
Embodiment 6
A kind of extra-weather-proof polyester resin for powder coating, the raw material of polyester resin include alcohol, acid, catalyst, antioxidant and promotion
Agent, the mol ratio of wherein described alcohol/acid is 1.2, and alcohol includes neopentyl glycol and trimethylolpropane, and it is total that trimethylolpropane accounts for alcohol
The 7wt% of quality；
Acid includes M-phthalic acid and 1,4 cyclohexanedicarboxylic acid；
Antioxidant accounts for acid, the 0.75wt% of alcohol gross mass, including antioxidant 1076 and irgasfos 168；
Catalyst is Mono-n-butyltin, and accelerator is ammonium salt or microcosmic salt.
In the present embodiment, the mol ratio of M-phthalic acid and Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic is 2:1, antioxidant 3114 and antioxygen
The mass ratio of agent 168 is 1:3.
The polyester resin of the above embodiment of the present invention, GPC results show that respectively molecular weight is 10909, and molecular weight distribution is
1.5, DSC results show that the polyester resin vitrification point of synthesis is 53 degrees Celsius, meet storage temperature requirement：The polyester of synthesis
The initial degradation temperature of resin is 293 degrees Celsius, and most degradation rate temperature is demonstrated by fine thermostable up to 442 degrees Celsius.
, compared with same kind of products at abroad performance, performance is preferable, specifically for this product：89 degree of glossiness, hardness 4H, secondary assistant etc.
0 grade of level all reaches the performance requirement of like product, and in addition compared with same kind of products at abroad performance more preferably, artificial acceleration is old for impact strength
Change test nearly 1500 hours, final light-protection rate is high.
Those of ordinary skill in the art should be understood：The discussion of any of the above embodiment is exemplary only, not
It is intended to imply that the scope of the present disclosure (including claim) is limited to these examples；Under the thinking of the present invention, above example
Or can also be combined between the technical characteristic in different embodiments, step can be realized with random order, and is existed such as
Many other changes of the different aspect of the upper described present invention, for their not offers in details simple and clear.Therefore, all
Within the spirit and principles in the present invention, any omission for being made, modification, equivalent, improvement etc. should be included in the present invention's
Within protection domain.
Claims (9)
1. a kind of extra-weather-proof polyester resin for powder coating, it is characterised in that the raw material of the polyester resin includes alcohol, acid, urges
Agent, antioxidant and accelerator, the mol ratio of wherein described alcohol/acid is 1.05-1.2, and the alcohol includes neopentyl glycol and three hydroxyls
Methylpropane, the trimethylolpropane account for the 1wt%-7wt% of alcohol gross mass；
The acid includes one or two in M-phthalic acid and 1,4 cyclohexanedicarboxylic acid；
The antioxidant accounts for acid, the 0.17wt%-0.75wt% of alcohol gross mass, including antioxidant 3114, antioxidant 1076 and antioxygen
One or more in agent 168；
The catalyst is Mono-n-butyltin, and the accelerator is ammonium salt or microcosmic salt.
2. extra-weather-proof polyester resin for powder coating according to claim 1, it is characterised in that the alcohol/acid mole
Than for 1.1.
3. extra-weather-proof polyester resin for powder coating according to claim 1, it is characterised in that the trimethylolpropane
Account for the 5wt% of alcohol gross mass.
4. extra-weather-proof polyester resin for powder coating according to claim 1, it is characterised in that the acid includes isophthalic two
The mol ratio of formic acid and Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic, the M-phthalic acid and Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic is（1-3）:（1-3）.
5. extra-weather-proof polyester resin for powder coating according to claim 4, it is characterised in that the M-phthalic acid and
The mol ratio of 1,4 cyclohexanedicarboxylic acid is 1:1.
6. extra-weather-proof polyester resin for powder coating according to claim 1, it is characterised in that the antioxidant accounts for acid alcohol
The 0.5wt% of gross mass.
7. extra-weather-proof polyester resin for powder coating according to claim 1, it is characterised in that the antioxidant includes resisting
Oxygen agent 3114 and irgasfos 168, the antioxidant 3114 with the mass ratio of irgasfos 168 is（1-2）:（1-2）.
8. extra-weather-proof polyester resin for powder coating according to claim 5, it is characterised in that the antioxidant 3114 with
The mass ratio of irgasfos 168 is 2:1.
9. extra-weather-proof polyester resin for powder coating according to claim 1, it is characterised in that the antioxidant includes resisting
Oxygen agent 1076 and irgasfos 168, the antioxidant 3114 with the mass ratio of irgasfos 168 is（1-2）:（1-2）.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611141447.6A CN106496532A (en) | 2016-12-12 | 2016-12-12 | A kind of extra-weather-proof polyester resin for powder coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611141447.6A CN106496532A (en) | 2016-12-12 | 2016-12-12 | A kind of extra-weather-proof polyester resin for powder coating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106496532A true CN106496532A (en) | 2017-03-15 |
Family
ID=58330830
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611141447.6A Pending CN106496532A (en) | 2016-12-12 | 2016-12-12 | A kind of extra-weather-proof polyester resin for powder coating |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108440745A (en) * | 2018-02-10 | 2018-08-24 | 谢新昇 | A kind of preparation method of weather-proof high temperature resistance polyester resin |
| CN109385054A (en) * | 2018-09-28 | 2019-02-26 | 吴亚琴 | A kind of preparation method of toughening heat-conducting plastic |
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| CN103059275A (en) * | 2012-12-28 | 2013-04-24 | 广州擎天材料科技有限公司 | A polyester resin used for TGIC cured transparent powder coatings |
| CN103613746A (en) * | 2013-12-04 | 2014-03-05 | 衡阳山泰化工有限公司 | Pure polyester resin for high weather-resistant outdoor powder coating and preparation method thereof |
| CN103613744A (en) * | 2013-10-22 | 2014-03-05 | 广州擎天材料科技有限公司 | Polyester resin used for TGIC-cured high-adhesive-force high-leveling-property powder coating and preparation method of the polyester resin |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108440745A (en) * | 2018-02-10 | 2018-08-24 | 谢新昇 | A kind of preparation method of weather-proof high temperature resistance polyester resin |
| CN109385054A (en) * | 2018-09-28 | 2019-02-26 | 吴亚琴 | A kind of preparation method of toughening heat-conducting plastic |
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