CN1858084A - Water nano composite polyester resin, its preparing method and use - Google Patents
Water nano composite polyester resin, its preparing method and use Download PDFInfo
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- CN1858084A CN1858084A CN 200610026687 CN200610026687A CN1858084A CN 1858084 A CN1858084 A CN 1858084A CN 200610026687 CN200610026687 CN 200610026687 CN 200610026687 A CN200610026687 A CN 200610026687A CN 1858084 A CN1858084 A CN 1858084A
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Abstract
The present invention relates to chemical technology, and is especially one kind of high hardness water nanometer composite polyester resin and its preparation process and application. Through a phonochemical process, nanometer particle with hydroxyl group or alkyl group in the surface is first reacted with polyol to graft polyol to the surface, and then in-situ reacted with polyol, dihydroxy carboxylic acid and carboxylic acid to synthesize composite polyester resin. Then, alkali is used to neutralize the hydrophilic carboxyl radical in polyester resin and water is added to prepare high hardness water nanometer composite polyester resin with stable performance. The said preparation process has easy grafting of polyester chain segment on the nanometer particle and homogeneous distribution of nanometer particle in polyester resin, and the prepared water nanometer composite polyester resin has good storing stability, high hardness and high transparency and may be used in preparing excellent coating material.
Description
Technical field
The present invention relates to chemical field, relate to a kind of high rigidity water-based nano composite polyester resin, its preparation method and application.
Background technology
Raising along with people's living standard; except having provide protection and high-decoration, also should have eco-friendly function to the requirement of coating and resin, water-base resin and water-borne coatings have many salient features and advantage; do not contain or only contain a small amount of solvent, nontoxic, safety.The aqueous dispersion type resin that a kind of automobile floating coat uses and the preparation method of coating thereof have been introduced as the patent CN1357582 of Xia Fanwu etc.; The patent CN1497032 of Gas Products Polymer Company has introduced a kind of preparation method who uses the water binder composition of waterborne polyester; US20040249077 has introduced a kind of preparation method who contains the aqueous film-forming compositions of isobutylene type monomers alternating copolymer.But compare with coating with solvent type resin, because membrane formation mechanism difference, what water-base resin and water-borne coatings formed films not as solvent type resin and coating densification, cause the defective of filming, in addition, the volatilization and the balance in the atmosphere of moisture also influence the performance of filming, and compare with coating with same or similar molecular structure solvent resin, are difficult to reach the performance of solvent type resin and coating.
Existing studies show that, the nanometer polymer compound coating is being that positive effect is arranged aspect the traditional performance (as ageing resistance, scoring resistance, wear resistance, anti-UV) that promotes coating, but direct blend of nanoparticle or in-situ polymerization are added in the resin, nanoparticle takes place to reunite and separate out easily, resin viscosity increases, can't prepare the particle modified resin of stabilized nano, more can't prepare the particle modified resin of water nano.If add the nanoparticle through surface modification in resin, owing to there is outer adding assistant to exist, resin property reduces.Adopt the nanoparticle in-situ polymerization to prepare water nano composite polyester resin and have not yet to see report.
Summary of the invention
The water nano composite polyester resin that the purpose of this invention is to provide a kind of high rigidity, low VOC, high-performance, environmental protection, safety.
Another object of the present invention provides the preparation method of above-mentioned water nano composite polyester resin.
A further object of the present invention provides the application of above-mentioned water nano composite polyester resin.
The invention provides a kind of water nano composite polyester resin.This resin is the nano composite polyester resin of Water-borne modification, nano composite polyester resin is to form with the carboxylic acid melt polymerization behind the nanoparticle surface graft polyol of or alkoxyl group hydroxyl on the surface, molecular weight is 1000-50000, acid number 20-70mgKOH/g, hydroxyl value 60-250mgKOH/g, nanoparticle content accounts for 1～15wt% of nano composite polyester resin gross weight, and the solid content of water nano composite polyester resin is 20-55wt%.
Specifically, water nano composite polyester resin of the present invention is made up of nano composite polyester resin, alkali, water, and satisfies two conditions: contain a kind of nano composite polyester resin; Contain a kind of alkali.
Nano composite polyester resin is made up of nanoparticle, polyvalent alcohol, dihydroxy carboxylic acids, carboxylic acid, and meets the following conditions, and A. contains a kind of nanoparticle of nanometer particle size at least; B. the dibasic alcohol, trivalent alcohol that contain a kind of molecular weight 60-1000 at least are as polyol component, and C. contains a kind of dihydroxy carboxylic acids; D. contain a kind of carboxylic acid at least.
The present invention also provides the preparation method of above-mentioned water nano composite polyester resin, be at the nanoparticle surface graft polyol, with polyvalent alcohol, carboxylic acid blended melting situ aggregation method synthesis of nano composite polyester resin, it is characterized in that this method may further comprise the steps again:
(1) nanoparticle and the polyvalent alcohol blend of the surface is hydroxyl or alkoxyl group adopt the sonochemistry synthetic method at the nanoparticle surface graft polyol; Control ultrasonic frequency 100-2000kHz, temperature of reaction 0-100 ℃, ultrasonic time 10-60 minute; The amount of substance of used polyvalent alcohol is the 20-100% of polyvalent alcohol mole total amount; The nanoparticle consumption is the 2-60wt% of polyvalent alcohol total amount;
(2) with (1) products therefrom and residue polyvalent alcohol, dihydroxy carboxylic acids, carboxylic acid blended melting polymerization synthesis of nano composite polyester resin; The reaction conditions of melt polymerization is 100-240 ℃, 2-12 hour; The amount of substance of used dihydroxy carboxylic acids is the 1-40% of polyvalent alcohol mole total amount and dihydroxy carboxylic acids amount of substance sum; The mol ratio of sour and pure and mild dihydroxy carboxylic acids amount of substance sum is 1: 2～1: 1.1;
(3) carboxylic nano composite polyester resin is neutralized with alkali, the consumption of alkali is that the degree of neutralization (degree of neutralization is the per-cent of the amount of acid in alkali and the resin) that makes acid in the nano composite polyester resin reaches 70-120%., and add water and make water nano composite polyester resin, solid content is 20-55wt%.
Specifically, nano composite polyester resin is made up of nanoparticle, polyvalent alcohol, dihydroxy carboxylic acids, carboxylic acid except that this dihydroxy carboxylic acids, and meets the following conditions simultaneously, and A. contains a kind of nanoparticle of nanometer particle size at least; B. the dibasic alcohol, trivalent alcohol that contain a kind of molecular weight 60-1000 at least are as polyol component, and C. contains a kind of dihydroxy carboxylic acids; D. contain a kind of carboxylic acid at least.
Among the above-mentioned preparation method, be that to adopt particle diameter be that the hydroxyl or/and alkoxyl group in 10-200nm, surface, particle diameter are the 1-3 kind in the inorganic nanometer oxide of 10-200nm.As nano silicon, nano-titanium oxide, nano aluminium oxide, nano-sized iron oxide, nano zircite, nano zine oxide.Nanoparticle content accounts for 1～15wt% of nano composite polyester resin gross weight.
Among the above-mentioned preparation method, acid is COOH: OH=1 with the mol ratio of alcohol (comprising dihydroxy carboxylic acids): 2～1: 1.1.
Among the above-mentioned preparation method, polyvalent alcohol is that molecular weight is dibasic alcohol or the trivalent alcohol of 60-1000, adopts 1-5 kind wherein.Used dibasic alcohol such as ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,3 butylene glycol, 1,6-hexylene glycol, 2,2-dimethyl-1, ammediol, glycol ether, 2-ethyl-2-propyl group-1, ammediol, 1,4-cyclohexanediol, cyclohexanedimethanol, polyoxyethylene glycol, polyether Glycols, used trivalent alcohol such as glycerol, TriMethylolPropane(TMP), polyether-tribasic alcohol etc.
Among the above-mentioned preparation method, dihydroxy carboxylic acids is a kind of in dihydroxyl alkanoic acid, the dihydroxyl aromatic acid, and consumption is the 1-40% of polyvalent alcohol and dihydroxy carboxylic acids mixture mole total amount.Used dihydroxy carboxylic acids such as dimethylol propionic acid, dimethylolpropionic acid, 9,10-dihydroxyl stearic acid, 2,4-resorcylic acid etc.
Among the above-mentioned preparation method, the polyvalent alcohol that adopt (1) be the dibasic alcohol of molecular weight 60-1000 or/and trivalent alcohol, consumption is the 20-100% of polyvalent alcohol mole total amount; The nanoparticle consumption is the 2-60wt% of polyvalent alcohol total amount.
Among the above-mentioned preparation method, carboxylic acid is the 1-5 kind in aliphatic dicarboxylic acid, alicyclic di-carboxylic acid, aromatic dicarboxylate, acid anhydrides, the caprolactone.As Succinic Acid, hexanodioic acid, nonane diacid, pimelic acid, suberic acid, 11 carbon dicarboxylic acids, SL-AH, tridecanyldicarboxylic acid, ten four-carbon dicarboxylic acids, 15 carbon dicarboxylic acids, 16-dicarboxylic acid, 18 carbon dicarboxylic acids, m-phthalic acid, terephthalic acid, phthalic acid, isophthalic anhydride, terephthalic anhydride, Tetra hydro Phthalic anhydride, hexahydrophthalic anhydride, 1,4 cyclohexanedicarboxylic acid, 6-caprolactone etc.
Among the above-mentioned preparation method, the preferred catalyzer that uses in the melt polymerization, catalyzer is any in antimony system, germanium system, titanium system, the tin system, as antimony acetate, antimony glycol, Germanium tetraacetate, stannous octoate, dibutyl tin laurate, tetra isopropyl titanate, titanium ethylene glycolate etc., consumption is the 0.01%-0.5wt% of pure and mild sour total amount.
Among the above-mentioned preparation method, the melt polymerization temperature is 100-240 ℃, reaction times 2-12 hour.
Among the above-mentioned preparation method, alkali is a kind of in metal hydroxides, ammonia, primary amine, secondary amine, the tertiary amine.As sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, primary amine such as isopropylamine, butylamine, thanomin, 3-amino-1-propyl alcohol, secondary amine such as morpholine, diethylamine, N-Mono Methyl Ethanol Amine, diethanolamine, tertiary amine such as Trimethylamine 99, N, N-dimethylethanolamine, triethylamine, three second propyl group amine, N, N-diethylethanolamine, N-ethylmorpholine.
Among the above-mentioned preparation method, the consumption of alkali is to make the degree of neutralization of acid in the nano composite polyester resin reach 70-120%.
The present invention also provides the application of above-mentioned water nano composite polyester resin.
The water nano composite polyester resin coated material of water nano composite polyester resin of the present invention and watersoluble closed multi isocyanate crosslinking reaction availability excellence.
The water nano composite polyester resin coated material of water nano composite polyester resin of the present invention and water-compatible amino resin crosslinking reaction availability excellence.
A kind of high rigidity water-based nano composite polyester resin that the present invention proposes and preparation method thereof, have the following advantages: the present invention adopts particle diameter 10-200nm, the surface is hydroxyl or/and the inorganic nanometer oxide particle of alkoxyl group, with the sonochemistry synthetic method at its surface grafting polyvalent alcohol, prepare as clear as crystal nanoparticle alcoholic solution, need not to add any reagent, can make nanoparticle in melt polymerization process, be dispersed in the resin system, directly form the polyester molecule coating layer on its surface, avoid the reunion of nanoparticle in resin, also reduce simultaneously the hydroxyl of nanoparticle surface and the hydrogen bond action of molecular resin greatly, resin viscosity is increased, guarantee the Water-borne modification of nano composite polyester resin and the sedimentation of nanoparticle can not occur.The water nano composite polyester resin concentration of preparation can reach more than 50%, and excellent storage stability is placed not sedimentation in a year at normal temperatures, and coating hardness height, wear resistance are good, have splendid workability.Adopt preparation method provided by the invention can obtain stable, that the transparency is good, high rigidity water-based nano composite polyester resin.
Description of drawings
Fig. 1 is transmission electron microscope (TEM) figure of sonochemistry synthesis of nano silicon-dioxide alcoholic solution.
Fig. 2 is that nano composite polyester resin prepares synoptic diagram.
Embodiment
Embodiment 1:
Thermometer is being housed, condenser, in the four-hole boiling flask of agitator, add 30 gram nano silicons, 1.0mol 1,4-butyleneglycol (90 gram), under the 1000rpm rotating speed, mixed 10 minutes, adopted sonochemistry synthetic 40 minutes, in the reaction, control ultrasonic frequency 1200kHz, 50 ℃ of temperature of reaction, add 1.0mol hexanodioic acid (114 gram), 0.8mol cyclohexanedimethanol (115.2 gram), 0.2mol dimethylol propionic acid (20.4 gram), the dibutyl tin laurate that adds 0.15 gram is warming up to 110-120 ℃ of reaction 2 hours, continues to be warming up to 160-180 ℃, reacted 4 hours, be warming up to 200-220 ℃ again, reacted 2 hours, obtain nano composite polyester resin.
Nano composite polyester resin slowly is chilled to 80 ℃, pour in the Scattered Kettle, add N, in the N-dimethylethanolamine and resin in acid, making degree of neutralization is 85%, adds the deionized water that measures, and making resin solid content is 50wt%, high-speed stirring is 30 minutes under the 2500rpm rotating speed, can prepare high rigidity water-based nano composite polyester resin.
Embodiment 2:
Thermometer is being housed, condenser, in the four-hole boiling flask of agitator, add 100 gram nano aluminium oxides, 0.5mol the polyoxyethylene glycol of molecular-weight average 400 (200 gram), under the 1000rpm rotating speed, mixed 20 minutes, adopted sonochemistry synthetic 60 minutes, in the reaction, control ultrasonic frequency 500kHz, 80 ℃ of temperature of reaction, add 0.6mol 11 carbon dicarboxylic acids (112.8 gram), 0.4mol 1,4-cyclohexane cyclohexanedimethanodibasic (68.8 gram), 0.5mol glycol ether (53 gram), 0.2mol 2-ethyl-2-propyl group-1, ammediol (29.2 gram), 0.1mol TriMethylolPropane(TMP) (13.4 gram), 0.3mol dimethylolpropionic acid (44.4 gram), the titanium ethylene glycolate that adds 0.10 gram, be warming up to 110-120 ℃ of reaction 3 hours, be warming up to 130-150 ℃ of reaction 3 hours, continue to be warming up to 170-190 ℃ of reaction 3 hours, obtain nano composite polyester resin.
Nano composite polyester resin slowly is chilled to 80 ℃, pour in the Scattered Kettle, add in 3-amino-1-propyl alcohol and the acid in the resin, making degree of neutralization is 100%, add the deionized water that measures, making resin solid content is 38wt%, and high-speed stirring is 50 minutes under the 3500rpm rotating speed, can prepare high rigidity water-based nano composite polyester resin.
Embodiment 3:
Thermometer is being housed, condenser, in the four-hole boiling flask of agitator, add 60 gram nano-titanium oxides, 1.0mol propylene glycol (76 gram), 0.2mol 1,6-hexylene glycol (23 gram), 0.1mol the polyether-tribasic alcohol of molecular-weight average 500 (50 gram), under the 1000rpm rotating speed, mixed 10 minutes, adopted sonochemistry synthetic 30 minutes, in the reaction, control ultrasonic frequency 1000kHz, 120 ℃ of temperature of reaction, add 0.5mol hexanodioic acid (57.0 gram), 0.3mol terephthalic acid (37.8 gram), 0.2mol isophthalic anhydride (29.6 gram), 0.1mol 2,4-resorcylic acid (13.8 gram) adds 3 Germanium tetraacetates that restrain, and is warming up to 110-120 ℃ of reaction 1 hour, be warming up to 130-150 ℃ of reaction 3 hours, continue to be warming up to 160-180 ℃ of reaction 3 hours, be warming up to 220-240 ℃ of reaction 2 hours, obtain nano composite polyester resin.
Nano composite polyester resin slowly is chilled to 90 ℃, pour in the Scattered Kettle, add in the isopropylamine and the acid in the resin, making degree of neutralization is 75%, add the deionized water that measures, making resin solid content is 30wt%, and high-speed stirring is 20 minutes under the 3000rpm rotating speed, can prepare high rigidity water-based nano composite polyester resin.
Embodiment 4:
Thermometer is being housed, condenser, in the four-hole boiling flask of agitator, add 10 gram nano zircites, 0.2mol the polyether-tribasic alcohol of molecular weight 1000 (100 gram), under the 1000rpm rotating speed, mixed 20 minutes, adopted the sonochemistry Synthetic 20 minute, in the reaction, control ultrasonic frequency 1500kHz, 80 ℃ of temperature of reaction, add 0.3mol Succinic Acid (35.4 gram), 0.4mol hexahydrophthalic anhydride (67.2 gram), 0.3mol nonane diacid (56.4 gram), 0.8mol cyclohexanedimethanol (115.2 gram), 0.4mol 9,10-dihydroxyl stearic acid (29.2 gram), the dibutyl tin laurate that adds 0.3 gram, be warming up to 150-170 ℃ of reaction 6 hours, continue to be warming up to 190-210 ℃ of reaction 3 hours, obtain nano composite polyester resin.
Nano composite polyester resin slowly is chilled to 70 ℃, pour in the Scattered Kettle, add in the ammoniacal liquor and the acid in the resin, making degree of neutralization is 120%, add the deionized water that measures, making resin solid content is 45wt%, and high-speed stirring is 30 minutes under the 2500rpm rotating speed, can prepare high rigidity water-based nano composite polyester resin.
Embodiment 5:
Thermometer is being housed, condenser, in the four-hole boiling flask of agitator, add 20 gram nano zine oxides, 0.5mol ethylene glycol (31 gram), 0.2mol the polyether Glycols of molecular weight 200 (40 gram), under the 1500rpm rotating speed, mixed 30 minutes, adopted sonochemistry synthetic 50 minutes, in the reaction, control ultrasonic frequency 1000kHz, 20 ℃ of temperature of reaction, add 1.0mol phthalic acid (150 gram), 0.5mol 2-ethyl-2-propyl group-1, ammediol (73 gram), 0.3mol dimethylol propionic acid (30.6 gram), the stannous octoate that adds 0.2 gram, be warming up to 100-120 ℃ of reaction 3 hours, be warming up to 140-160 ℃ of reaction 3 hours, continue to be warming up to 180-200 ℃ of reaction 2 hours, be warming up to 220-240 ℃ of reaction 1 hour, obtain nano composite polyester resin.
Nano composite polyester resin slowly is chilled to 90 ℃, pour in the Scattered Kettle, add in the N-Mono Methyl Ethanol Amine and the acid in the resin, making degree of neutralization is 90%, add the deionized water that measures, making resin solid content is 45wt%, and high-speed stirring is 40 minutes under the 3000rpm rotating speed, can prepare high rigidity water-based nano composite polyester resin.
Embodiment 6:
Thermometer is being housed, condenser, in the four-hole boiling flask of agitator, add 75 gram nano silicons, 0.2mol the polyoxyethylene glycol of molecular weight 800 (160 gram), under the 1000rpm rotating speed, mixed 20 minutes, adopted sonochemistry synthetic 40 minutes, in the reaction, control ultrasonic frequency 2000kHz, 100 ℃ of temperature of reaction, add 0.8mol isophthalic anhydride (118.4 gram), 0.2mol 15 carbon dicarboxylic acids (48 gram), 0.8mol 1,5-hexylene glycol (94.4 gram), 0.4mol dimethylolpropionic acid (59.2 gram), the dibutyl tin laurate that adds 0.4 gram, be warming up to 140-160 ℃ of reaction 5 hours, continue to be warming up to 190-210 ℃ of reaction 4 hours, obtain nano composite polyester resin.
Nano composite polyester resin slowly is chilled to 80 ℃, pour in the Scattered Kettle, add in the N-ethylmorpholine and the acid in the resin, making degree of neutralization is 80%, add the deionized water that measures, making resin solid content is 40wt%, and high-speed stirring is 30 minutes under the 3000rpm rotating speed, can prepare high rigidity water-based nano composite polyester resin.
Claims (10)
1. water nano composite polyester resin, it is characterized in that, nano composite polyester resin is to form with the carboxylic acid melt polymerization behind the nanoparticle surface graft polyol of or alkoxyl group hydroxyl on the surface, its molecular weight is 1000-50000, acid number 20-70mgKOH/g, hydroxyl value 60-250mgKOH/g, nanoparticle content accounts for 1～15wt% of nano composite polyester resin gross weight, and the solid content of water nano composite polyester resin is 20-55wt%.
2. the preparation method of water nano composite polyester resin according to claim 1, it is characterized in that this method is at the nanoparticle surface graft polyol, again with residue polyvalent alcohol, dihydroxy carboxylic acids, carboxylic acid blended melting situ aggregation method synthesis of nano composite polyester resin; This method specifically may further comprise the steps:
(1) nanoparticle and the polyvalent alcohol blend of the surface is hydroxyl or alkoxyl group adopt the sonochemistry synthetic method at the nanoparticle surface graft polyol; Control ultrasonic frequency 100-2000kHz, temperature of reaction 0-100 ℃, ultrasonic time 10-60 minute; The amount of substance of used polyvalent alcohol is the 20-100% of polyvalent alcohol mole total amount; The nanoparticle consumption is the 2-60wt% of polyvalent alcohol total amount;
(2) with (1) products therefrom and residue polyvalent alcohol, dihydroxy carboxylic acids, carboxylic acid blended melting polymerization synthesis of nano composite polyester resin; The reaction conditions of melt polymerization is 100-240 ℃, 2-12 hour; The molar weight of used dihydroxy carboxylic acids accounts for the 1-40% of dihydroxy carboxylic acids and polyvalent alcohol molar weight sum; The molar weight of acid and the ratio of pure and mild dihydroxy carboxylic acids molar weight sum are 1: 1.1～2;
(3) with the neutralization of carboxylic nano composite polyester resin and alkali, the consumption of alkali is to make the degree of neutralization of acid in the nano composite polyester resin reach 70-120%, and adds water and make water nano composite polyester resin, and solid content is 20-55wt%.
3. preparation method according to claim 2 is characterized in that hydroxyl or/and alkoxyl group, particle diameter are 1-3 kind in the inorganic nanometer oxide of 10-200nm for the surface for the nanoparticle that adopts.
4. preparation method according to claim 3 is characterized in that the nanoparticle that adopts is the 1-3 kind in nano silicon, nano-titanium oxide, nano aluminium oxide, nano-sized iron oxide, nano zircite, the nano zine oxide.
5. preparation method according to claim 2 is characterized in that the polyvalent alcohol that adopts is the dibasic alcohol of molecular weight 60-1000, the 1-5 kind in the trivalent alcohol.
6. method according to claim 2 is characterized in that used dihydroxy carboxylic acids is a kind of in dihydroxyl alkanoic acid, the dihydroxyl aromatic acid.
7. preparation method according to claim 2 is characterized in that carboxylic acid is the 1-5 kind in aliphatic dicarboxylic acid, alicyclic di-carboxylic acid, aromatic dicarboxylate, acid anhydrides, the caprolactone.
8. preparation method according to claim 2 is characterized in that using in the melt polymerization catalyzer, and catalyzer is a kind of of antimony system, germanium system, titanium system, tin series catalysts, and consumption is the 0.01-0.5wt% of pure and mild sour total amount.
9. preparation method according to claim 2 is characterized in that alkali is a kind of in metal hydroxides, ammonia, primary amine, secondary amine, the tertiary amine.
10. according to the application of the described water nano composite polyester resin of claim 1, it is characterized in that this resin and watersoluble closed polyisocyanates or water-compatible amino resin composition coated material.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101544768B (en) * | 2008-03-27 | 2012-10-31 | 施乐公司 | Latex preparation process |
| CN105622908A (en) * | 2014-11-28 | 2016-06-01 | 合众（佛山）化工有限公司 | Preparation method of nano-SiO2 modified alkyd resin |
| CN109196015A (en) * | 2016-04-20 | 2019-01-11 | 埃莱万斯可再生能源科学股份有限公司 | Polyester and production and preparation method thereof derived from renewable source |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2369365B (en) * | 2000-09-01 | 2004-05-19 | Nippon Paint Co Ltd | Water-borne coating composition and method of forming multilayer coating film |
| CN100556969C (en) * | 2004-12-27 | 2009-11-04 | 复旦大学 | A kind of have changeable colors along with angle effect metal finish paint and preparation method thereof |
-
2006
- 2006-05-18 CN CNB2006100266871A patent/CN100427526C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101544768B (en) * | 2008-03-27 | 2012-10-31 | 施乐公司 | Latex preparation process |
| CN105622908A (en) * | 2014-11-28 | 2016-06-01 | 合众（佛山）化工有限公司 | Preparation method of nano-SiO2 modified alkyd resin |
| CN109196015A (en) * | 2016-04-20 | 2019-01-11 | 埃莱万斯可再生能源科学股份有限公司 | Polyester and production and preparation method thereof derived from renewable source |
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