CN106883399B - A kind of silicone modified polyester resin and preparation method thereof - Google Patents
A kind of silicone modified polyester resin and preparation method thereof Download PDFInfo
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- CN106883399B CN106883399B CN201710264563.5A CN201710264563A CN106883399B CN 106883399 B CN106883399 B CN 106883399B CN 201710264563 A CN201710264563 A CN 201710264563A CN 106883399 B CN106883399 B CN 106883399B
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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
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
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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
- C08G63/66—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
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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
- C08G63/66—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
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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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
- C08G63/78—Preparation processes
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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
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
Abstract
The present invention relates to a kind of silicone modified polyester resins and preparation method thereof, the resin includes following components in parts by weight: 41~55 parts of multicomponent organic acid, 34~48 parts of polyalcohol, 12~25 parts of silicone intermediate, 0.5~1 part of catalyst, 0.1~0.8 part of heat stabilizer, 30~40 parts of solvent.The silicone modified polyester resin one-component service performance is excellent, with excellent adhesive force and high temperature resistance, the preparation method processing step is simple, lower production costs, with reasonable modified scheme, it is uniformly distributed in organosilicon in the structure of polyester resin, improves the comprehensive performance of product.
Description
Technical field
The invention belongs to macromolecule chemical industry preparation technical fields, and in particular to a kind of silicone modified polyester resin and its system
Preparation Method.
Background technique
With the rapid development of modern industry, resin material shows impayable excellent performance, makes it in chemical industry, boat
The every field such as empty space flight, electric, light industry, machinery, building are widely used.Continuously improving for resin is become
The emphasis of technical field of macromolecules, while different types of resin is modified, make its performance complement, has become high score
The hot spot of son development.
Organic siliconresin and polyester resin are extremely important two class, organic siliconresin in resin material in chemical field
In contain Si-O-Si structure, have excellent oxidative resistance, weatherability, heat resistance, chemicals-resistant, radiation hardness, surface free energy
The characteristics such as low, electrical isolation.But organic siliconresin needs hot setting, poor adhesive force, poor solvent resistance, and mechanical strength is not high；It is poly-
Ester resin has many advantages, such as good chemical corrosion resistance, adhesive force, flexibility, is provided simultaneously with excellent physical mechanical performance, but its
Heat-resisting quantity and application property are poor.Though two resinoids have certain characteristic, there are certain defect, be not achieved it is higher it is desirable that
It asks.
Therefore research is modified to the two, prepares silicone modified polyester resin, so that the two is had complementary advantages, can be improved
The comprehensive performance of resin, extension resin use field, meet industrial development demand.But current organosilicon modified polyester needs mostly
Isocyanate curing agent of arranging in pairs or groups uses, and is just able to satisfy performance requirement, keeps construction complicated and often results in waste.
Therefore silicone modified polyester resin and preparation method thereof has yet to be improved and developed.
Summary of the invention
For technical problem of the existing technology, the present invention provides a kind of silicone modified polyester resin and its preparation side
Method, the silicone modified polyester resin one-component service performance is excellent, has excellent high temperature resistance, the preparation method
Processing step is simple, lower production costs, with reasonable modified scheme, organosilicon is made to be uniformly distributed in the structure of polyester resin
On, improve the comprehensive performance of product.
To reach above-mentioned technical effect, the invention adopts the following technical scheme:
It is an object of the present invention to provide a kind of silicone modified polyester resin, the resin includes in parts by weight
Following components:
Wherein, the mass parts of multicomponent organic acid can be 41 parts, 42 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 parts, 49 parts,
50 parts, 51 parts, 52 parts, 53 parts, 54 parts or 55 parts etc.；The mass parts of polyalcohol can be 34 parts, 35 parts, 36 parts, 37 parts, 38
Part, 39 parts, 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts or 48 parts etc.；The mass parts of silicone intermediate
It can be 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts or 25 parts
Deng；The mass parts of catalyst can be 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part or 1 part etc.；The mass parts of heat stabilizer
It can be 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part or 0.8 part etc.；The mass parts of solvent can be 30
Part, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts or 40 parts etc., it is not limited to cited
Numerical value, other are that the numerical value enumerated is equally applicable in above each numberical range.
As currently preferred technical solution, the multicomponent organic acid include terephthalic acid (TPA), phthalic acid or oneself
Any one in diacid or at least two combination, the combination is typical but non-limiting example has: phthalic acid and adjacent benzene two
The combination of formic acid, combination of phthalic acid and adipic acid etc., the combination of adipic acid and phthalic acid or phthalic acid, adjacent benzene two
Formic acid and the combination of adipic acid etc..
Preferably, the polyalcohol include any one in neopentyl glycol, diglycol or trimethylolpropane or
At least two combination, the combination is typical but non-limiting example has: the combination of neopentyl glycol and diglycol, a contracting
The combination of diethylene glycol and trimethylolpropane, the combination of trimethylolpropane and neopentyl glycol or neopentyl glycol, a contracting diethyl
The combination etc. of two pure and mild trimethylolpropanes.
As currently preferred technical solution, the silicone intermediate includes DOW CORNING 3037 and/or DOW CORNING Z-
6018。
Two kinds of silicone intermediates have excellent thermo oxidative stability, can effective modified polyester resin, raising changes
Property resin heat-resisting, weatherability, make modified resin have excellent wetability, improve the dispersing uniformity of paint filler.
As currently preferred technical solution, the catalyst includes stannous octoate.
Preferably, the heat stabilizer includes triphenyl phosphite.
Preferably, the solvent includes toluene and/or dimethylbenzene.
The second purpose of the present invention is to provide a kind of preparation methods of above-mentioned resin, which is characterized in that the preparation method
The following steps are included:
(1) multicomponent organic acid, polyalcohol, catalyst and solvent are mixed, is warming up to the first reaction under a shielding gas
At a temperature of react, heat stabilizer is added and is warming up to the reaction of the second reaction temperature, polynary alcohol and solvent is added after cooling, is warming up to the
Three reaction temperatures, obtain polyester resin solution；
(2) polyester resin solution, silicone intermediate, heat stabilizer, catalyst and the solvent for obtaining step (1) are mixed
It closes, is warming up to the reaction of the 4th reaction temperature under a shielding gas, then be warming up to the reaction of the 5th reaction temperature, it is anti-being warming up to the 6th
Thermotonus is answered, silicone modified polyester resin is obtained.
Silicone modified polyester resin of the invention has synthesis technology simple, and preparation speed is fast, and volume production security effectiveness is high,
This method preparation silicone modified polyester resin have excellent ageing-resistant xanthochromia, wearability, water boiling resistance, mechanicalness and
Suitable apparent activation energy.
As currently preferred technical solution, step (1) first reaction temperature is 160~180 DEG C, such as 160 DEG C,
162 DEG C, 165 DEG C, 168 DEG C, 170 DEG C, 172 DEG C, 175 DEG C, 178 DEG C or 180 DEG C etc., it is not limited to cited numerical value,
Other are that the numerical value enumerated is equally applicable in the numberical range.
Preferably, the time reacted under step (1) first reaction temperature be 40~60min, as 40min, 42min,
45min, 48min, 50min, 52min, 55min, 58min or 60min etc., it is not limited to cited numerical value, the numerical value
Other are that the numerical value enumerated is equally applicable in range.
Preferably, step (1) heating rate for being warming up to the first reaction temperature is 4~6 DEG C/min, such as 4 DEG C/min,
4.2 DEG C/min, 4.5 DEG C/min, 4.8 DEG C/min, 5 DEG C/min, 5.2 DEG C/min, 5.5 DEG C/min, 5.8 DEG C/min or 6 DEG C/min
Deng it is not limited to cited numerical value, other are that the numerical value enumerated is equally applicable in the numberical range.
Preferably, step (1) described protective gas includes the group of any one in nitrogen, helium or argon gas or at least two
It closes, the combination is typical but non-limiting example has: the combination of nitrogen and argon gas, the combination of argon gas and helium, helium and nitrogen
Combination or the combination of nitrogen, helium or argon gas etc..
Preferably, step (1) second reaction temperature be 210~250 DEG C, such as 210 DEG C, 215 DEG C, 220 DEG C, 225 DEG C,
230 DEG C, 235 DEG C, 240 DEG C, 245 DEG C or 250 DEG C etc., it is not limited to cited numerical value, interior other of the numberical range are
The numerical value enumerated is equally applicable.
Preferably, the time reacted under step (1) second reaction temperature be 40~60min, as 40min, 42min,
45min, 48min, 50min, 52min, 55min, 58min or 60min etc., it is not limited to cited numerical value, the numerical value
Other are that the numerical value enumerated is equally applicable in range.
Preferably, step (1) heating rate for being warming up to the second reaction temperature is 0.5~2 DEG C/min, such as 0.5 DEG C/
Min, 0.6 DEG C/min, 0.8 DEG C/min, 1 DEG C/min, 1.2 DEG C/min, 1.5 DEG C/min, 1.8 DEG C/min or 2 DEG C/min etc., but simultaneously
It is not limited only to cited numerical value, other are that the numerical value enumerated is equally applicable in the numberical range.
Preferably, water is steamed during reacting under step (2) second reaction temperature simultaneously.
As currently preferred technical solution, the temperature of step (1) described cooling is 160~200 DEG C, such as 160 DEG C,
165 DEG C, 170 DEG C, 175 DEG C, 180 DEG C, 185 DEG C, 190 DEG C, 195 DEG C or 200 DEG C etc., it is not limited to cited numerical value,
Other are that the numerical value enumerated is equally applicable in the numberical range.
Preferably, the quality for the polyalcohol that the polyalcohol being added after step (1) described cooling is added before reacting with step (1)
Than for 1:(16~23), such as 1:16,1:17,1:18,1:19,1:20,1:21,1:22 or 1:23, it is not limited to listed
The numerical value of act, other are that the numerical value enumerated is equally applicable in the numberical range.
Preferably, the mass ratio for the multi-solvent that the solvent being added after step (1) described cooling is added before reacting with step (1)
For 1:(5~10), such as 1:5,1:6,1:7,1:8,1:9 or 1:10, it is not limited to cited numerical value, the numerical value model
Other are that the numerical value enumerated is equally applicable in enclosing.
Preferably, step (1) the third reaction temperature be 210~240 DEG C, such as 210 DEG C, 215 DEG C, 220 DEG C, 225 DEG C,
230 DEG C, 235 DEG C or 240 DEG C etc., it is not limited to cited numerical value, other are that the numerical value enumerated is same in the numberical range
Sample is applicable in.
Preferably, step (1) heating rate for being warming up to third reaction temperature is 0.3~2 DEG C/min, such as 0.3 DEG C/
Min, 0.5 DEG C/min, 0.8 DEG C/min, 1 DEG C/min, 1.2 DEG C/min, 1.5 DEG C/min, 1.8 DEG C/min or 2 DEG C/min etc., but simultaneously
It is not limited only to cited numerical value, other are that the numerical value enumerated is equally applicable in the numberical range.
The heat stabilizer that the heat stabilizer being added as currently preferred technical solution, step (2) and step (1) are added
Mass ratio be 1:(1~3), such as 1:1,1:1.5,1:2,1:2.5 or 1:3, it is not limited to cited numerical value, the number
Other are that the numerical value enumerated is equally applicable within the scope of value.
Preferably, the mass ratio for the catalyst that the catalyst and step (1) that step (2) is added are added is (1~2.5): 1,
Such as 1:1,1.25:1,1.5:1,1.75:1,2:1,2.25:1 or 2.5:1, it is not limited to cited numerical value, the numerical value
Other are that the numerical value enumerated is equally applicable in range.
Preferably, the mass ratio for the solvent that the solvent and step (1) that step (2) is added are added is 1:(3.5~9), such as 1:
3.5,1:4,1:4.5,1:5,1:6,1:7,1:8 or 1:9 etc., it is not limited to cited numerical value, in the numberical range its
He is that the numerical value enumerated is equally applicable.
As currently preferred technical solution, step (2) the 4th reaction temperature is 160~180 DEG C, such as 160 DEG C,
162 DEG C, 165 DEG C, 168 DEG C, 170 DEG C, 172 DEG C, 175 DEG C, 178 DEG C or 180 DEG C etc., it is not limited to cited numerical value,
Other are that the numerical value enumerated is equally applicable in the numberical range.
Preferably, step (2) reaction time under the 4th reaction temperature is 45~75min, as 45min,
50min, 55min, 60min, 65min, 70min or 75min etc., it is not limited to cited numerical value, in the numberical range
Other are that the numerical value enumerated is equally applicable.
Preferably, step (2) the 5th reaction temperature be 185~195 DEG C, such as 185 DEG C, 186 DEG C, 187 DEG C, 188 DEG C,
189 DEG C, 190 DEG C, 191 DEG C, 192 DEG C, 193 DEG C, 194 DEG C or 195 DEG C etc., it is not limited to cited numerical value, the numerical value
Other are that the numerical value enumerated is equally applicable in range.
Preferably, step (2) reaction time under the 5th reaction temperature is 45~75min, as 45min,
50min, 55min, 60min, 65min, 70min or 75min etc., it is not limited to cited numerical value, in the numberical range
Other are that the numerical value enumerated is equally applicable.
Preferably, step (2) the 6th reaction temperature be 200~220 DEG C, such as 200 DEG C, 202 DEG C, 205 DEG C, 208 DEG C,
210 DEG C, 212 DEG C, 215 DEG C, 218 DEG C or 220 DEG C etc., it is not limited to cited numerical value, interior other of the numberical range are
The numerical value enumerated is equally applicable.
Preferably, step (2) reaction under the 6th reaction temperature to reaction stops water outlet.
As currently preferred technical solution, the described method comprises the following steps:
(1) multicomponent organic acid, polyalcohol, catalyst and solvent are mixed, is warming up to 160~180 under a shielding gas
40~60min is reacted at DEG C, and heat stabilizer is added and is warming up to 210~250 DEG C of 40~60min of reaction, while steaming water, is cooled to
Polynary alcohol and solvent is added after 160~200 DEG C, is warming up to 210~240 DEG C of reactions, obtains polyester resin solution；
(2) polyester resin solution, silicone intermediate, heat stabilizer, catalyst and the solvent for obtaining step (1) are mixed
It closes, is warming up to 160~180 DEG C of 45~75min of reaction under a shielding gas, then be warming up to 185~195 DEG C of 45~75min of reaction,
200~220 DEG C of reactions are being warming up to, reaction to reaction stops water outlet, obtains silicone modified polyester resin.
Compared with prior art, the present invention at least has the advantages that
(1) present invention provides a kind of silicone modified polyester resin, and the resin one-component service performance is excellent, has excellent
Different adhesive force and high temperature resistance, adhesive force are 0 grade under GB/T 9826-1993 standard, and 2h is toasted at 320 DEG C without change
It is yellow, crack and the phenomenon that becomes fragile；
(2) present invention provides a kind of preparation method of silicone modified polyester resin, the preparation method processing step letter
Single, lower production costs are uniformly distributed in organosilicon in the structure of polyester resin, improve with reasonable modified scheme
The comprehensive performance of product.
Specific embodiment
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in the understanding present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
A kind of preparation method of silicone modified polyester resin, the described method comprises the following steps:
(1) 42 parts of multicomponent organic acids, 33 parts of polyalcohols, 0.2 part of catalyst and 28 parts of dimethylbenzene are mixed, is protected in nitrogen
It is warming up at 170 DEG C under shield with 4 DEG C/min and reacts 50min, 0.2 part of heat stabilizer is added with 1 DEG C/min and is warming up to 230 DEG C of reactions
50min, while water is steamed, 2 parts of polyalcohols and 3 parts of dimethylbenzene are added after being cooled to 180 DEG C, are warming up to 220 DEG C instead with 1 DEG C/min
It answers, 5 parts of toluene is added after reaction and obtain polyester resin solution；
(2) 65 parts, 14 parts silicone intermediates of polyester resin solution for obtaining step (1), 0.2 part of heat stabilizer, 0.3
Part catalyst and 4 parts of dimethylbenzene mixing, are warming up to 170 DEG C of reaction 60min, then be warming up to 185 DEG C of reactions under nitrogen protection
60min, then 200 DEG C of reactions are warming up to, reaction to reaction stops water outlet, obtains silicone modified polyester resin.
In the present embodiment, multicomponent organic acid is 25 parts of terephthalic acid (TPA), 10 parts of phthalic acid, 7 parts of adipic acid
In the present embodiment, polyalcohol is 28 parts of neopentyl glycol, 5 parts of diglycol, 2 parts of trimethylolpropane.
In the present embodiment, silicone intermediate is 3,037 14 parts of road DOW CORNING.
In the present embodiment, catalyst is 0.5 part of stannous octoate.
In the present embodiment, heat stabilizer is 0.4 part of triphenyl phosphite.
In the present embodiment, solvent is 5 parts of toluene, 35 parts of dimethylbenzene.
Embodiment 2
A kind of preparation method of silicone modified polyester resin, the described method comprises the following steps:
(1) 46 parts of multicomponent organic acids, 36 parts of polyalcohols, 0.3 part of catalyst and 20 parts of dimethylbenzene are mixed, is protected in nitrogen
It is warming up at 170 DEG C under shield with 4 DEG C/min and reacts 50min, 0.2 part of heat stabilizer is added with 1 DEG C/min and is warming up to 230 DEG C of reactions
50min, while water is steamed, 2 parts of polyalcohols and 4 parts of dimethylbenzene are added after being cooled to 180 DEG C, are warming up to 220 DEG C instead with 1 DEG C/min
It answers, 5 parts of toluene is added after reaction and obtain polyester resin solution；
(2) 65 parts, 18 parts silicone intermediates of polyester resin solution for obtaining step (1), 0.2 part of heat stabilizer, 0.4
Part catalyst and 6 parts of dimethylbenzene mixing, are warming up to 170 DEG C of reaction 60min, then be warming up to 185 DEG C of reactions under nitrogen protection
60min, then 200 DEG C of reactions are warming up to, reaction to reaction stops water outlet, obtains silicone modified polyester resin.
In the present embodiment, multicomponent organic acid is 28 parts of terephthalic acid (TPA), 10 parts of phthalic acid, 8 parts of adipic acid.
In the present embodiment, polyalcohol is 29 parts of neopentyl glycol, 7 parts of diglycol, 2 parts of trimethylolpropane.
In the present embodiment, silicone intermediate is 3,037 18 parts of road DOW CORNING.
In the present embodiment, catalyst is 0.7 part of stannous octoate.
In the present embodiment, heat stabilizer is 0.4 part of triphenyl phosphite.
In the present embodiment, solvent is 5 parts of toluene, 30 parts of dimethylbenzene.
Embodiment 3
A kind of preparation method of silicone modified polyester resin, the described method comprises the following steps:
(1) 52 parts of multicomponent organic acids, 40 parts of polyalcohols, 0.3 part of catalyst and 20 parts of dimethylbenzene are mixed, is protected in nitrogen
It is warming up at 170 DEG C under shield with 4 DEG C/min and reacts 50min, 0.2 part of heat stabilizer is added with 1 DEG C/min and is warming up to 230 DEG C of reactions
50min, while water is steamed, 2 parts of polyalcohols and 5 parts of dimethylbenzene are added after being cooled to 180 DEG C, are warming up to 220 DEG C instead with 1 DEG C/min
It answers, 5 parts of toluene is added after reaction and obtain polyester resin solution；
(2) 65 parts, 22 parts silicone intermediates of polyester resin solution for obtaining step (1), 0.2 part of heat stabilizer, 0.7
Part catalyst and 8 parts of dimethylbenzene mixing, are warming up to 170 DEG C of reaction 60min, then be warming up to 185 DEG C of reactions under nitrogen protection
60min, then 200 DEG C of reactions are warming up to, reaction to reaction stops water outlet, obtains silicone modified polyester resin.
In the present embodiment, multicomponent organic acid is 30 parts of terephthalic acid (TPA), 15 parts of phthalic acid, 7 parts of adipic acid.
In the present embodiment, polyalcohol is 30 parts of neopentyl glycol, 10 parts of diglycol, 2 parts of trimethylolpropane.
In the present embodiment, silicone intermediate is 3,037 22 parts of road DOW CORNING.
In the present embodiment, catalyst is 1 part of stannous octoate.
In the present embodiment, heat stabilizer is 0.4 part of triphenyl phosphite.
In the present embodiment, solvent is 5 parts of toluene, 33 parts of dimethylbenzene.
Embodiment 4
A kind of preparation method of silicone modified polyester resin, the described method comprises the following steps:
(1) 45 parts of multicomponent organic acids, 34 parts of polyalcohols, 0.2 part of catalyst and 20 parts of dimethylbenzene are mixed, is protected in nitrogen
It is warming up at 170 DEG C under shield with 4 DEG C/min and reacts 50min, 0.2 part of heat stabilizer is added with 1 DEG C/min and is warming up to 230 DEG C of reactions
50min, while water is steamed, 2 parts of polyalcohols and 3 parts of dimethylbenzene are added after being cooled to 180 DEG C, are warming up to 220 DEG C instead with 1 DEG C/min
It answers, 5 parts of toluene is added after reaction and obtain polyester resin solution；
(2) 68 parts, 16 parts silicone intermediates of polyester resin solution for obtaining step (1), 0.2 part of heat stabilizer, 0.4
Part catalyst and 4 parts of dimethylbenzene mixing, are warming up to 170 DEG C of reaction 60min, then be warming up to 185 DEG C of reactions under nitrogen protection
60min, then 200 DEG C of reactions are warming up to, reaction to reaction stops water outlet, obtains silicone modified polyester resin.
In the present embodiment, multicomponent organic acid is 30 parts of terephthalic acid (TPA), 10 parts of phthalic acid, 5 parts of adipic acid.
In the present embodiment, polyalcohol is 27 parts of neopentyl glycol, 7 parts of diglycol, 2 parts of trimethylolpropane.
In the present embodiment, silicone intermediate is 16 parts of road DOW CORNING Z-6018.
In the present embodiment, catalyst is 0.6 part of stannous octoate.
In the present embodiment, heat stabilizer is 0.4 part of triphenyl phosphite.
In the present embodiment, solvent is 5 parts of toluene, 27 parts of dimethylbenzene.
Embodiment 5
A kind of preparation method of silicone modified polyester resin, the described method comprises the following steps:
(1) 50 parts of multicomponent organic acids, 36 parts of polyalcohols, 0.3 part of catalyst and 22 parts of dimethylbenzene are mixed, is protected in nitrogen
It is warming up at 170 DEG C under shield with 4 DEG C/min and reacts 50min, 0.2 part of heat stabilizer is added with 1 DEG C/min and is warming up to 230 DEG C of reactions
50min, while water is steamed, 2 parts of polyalcohols and 3 parts of dimethylbenzene are added after being cooled to 180 DEG C, are warming up to 220 DEG C instead with 1 DEG C/min
It answers, 5 parts of toluene is added after reaction and obtain polyester resin solution；
(2) 68 parts, 20 parts silicone intermediates of polyester resin solution for obtaining step (1), 0.2 part of heat stabilizer, 0.5
Part catalyst and 6 parts of dimethylbenzene mixing, are warming up to 170 DEG C of reaction 60min, then be warming up to 185 DEG C of reactions under nitrogen protection
60min, then 200 DEG C of reactions are warming up to, reaction to reaction stops water outlet, obtains silicone modified polyester resin.
In the present embodiment, multicomponent organic acid is 32 parts of terephthalic acid (TPA), 12 parts of phthalic acid, 6 parts of adipic acid.
In the present embodiment, polyalcohol is 29 parts of neopentyl glycol, 7 parts of diglycol, 2 parts of trimethylolpropane.
In the present embodiment, silicone intermediate is 20 parts of road DOW CORNING Z-6018.
In the present embodiment, catalyst is 0.8 part of stannous octoate.
In the present embodiment, heat stabilizer is 0.4 part of triphenyl phosphite.
In the present embodiment, solvent is 5 parts of toluene, 31 parts of dimethylbenzene.
Embodiment 6
A kind of preparation method of silicone modified polyester resin, the described method comprises the following steps:
(1) 41 parts of multicomponent organic acids, 32 parts of polyalcohols, 0.2 part of catalyst and 18 parts of dimethylbenzene are mixed, is protected in nitrogen
It is warming up at 160 DEG C under shield with 5 DEG C/min and reacts 50min, 0.05 part of heat stabilizer is added with 1.5 DEG C/min and is warming up to 210 DEG C
50min is reacted, while steaming water, 2 parts of polyalcohols and 3 parts of dimethylbenzene are added after being cooled to 160 DEG C, are warming up to 1.5 DEG C/min
210 DEG C of reactions are added 5 parts of toluene and obtain polyester resin solution after reaction；
(2) 68 parts, 12 parts silicone intermediates of polyester resin solution for obtaining step (1), 0.05 part of heat stabilizer,
0.3 part of catalyst and 5 parts of dimethylbenzene mixing, are warming up to 160 DEG C of reaction 75min, then be warming up to 185 DEG C instead under nitrogen protection
45min is answered, then is warming up to 200 DEG C of reactions, reaction to reaction stops water outlet, obtains silicone modified polyester resin.
In the present embodiment, multicomponent organic acid be 41 parts of terephthalic acid (TPA),.
In the present embodiment, polyalcohol is 34 parts of neopentyl glycol.
In the present embodiment, silicone intermediate is 12 parts of road DOW CORNING Z-6018.
In the present embodiment, catalyst is 0.5 part of stannous octoate.
In the present embodiment, heat stabilizer is 0.1 part of triphenyl phosphite.
In the present embodiment, solvent is 5 parts of toluene, 26 parts of dimethylbenzene.
Embodiment 7
A kind of preparation method of silicone modified polyester resin, the described method comprises the following steps:
(1) 55 parts of multicomponent organic acids, 46 parts of polyalcohols, 0.5 part of catalyst and 24 parts of dimethylbenzene are mixed, is protected in nitrogen
It is warming up at 180 DEG C under shield with 6 DEG C/min and reacts 40min, 0.6 part of heat stabilizer is added with 2 DEG C/min and is warming up to 250 DEG C of reactions
40min, while water is steamed, 2 parts of polyalcohols and 3 parts of dimethylbenzene are added after being cooled to 200 DEG C, are warming up to 240 DEG C instead with 2 DEG C/min
It answers, 5 parts of toluene is added after reaction and obtain polyester resin solution；
(2) 68 parts, 25 parts silicone intermediates of polyester resin solution for obtaining step (1), 0.2 part of heat stabilizer, 0.5
Part catalyst and 8 parts of dimethylbenzene mixing, are warming up to 180 DEG C of reaction 45min, then be warming up to 195 DEG C of reactions under nitrogen protection
45min, then 220 DEG C of reactions are warming up to, reaction to reaction stops water outlet, obtains silicone modified polyester resin.
In the present embodiment, multicomponent organic acid is 55 parts of phthalic acid.
In the present embodiment, polyalcohol is 48 parts of diglycol.
In the present embodiment, silicone intermediate is 3,037 25 parts of road DOW CORNING.
In the present embodiment, catalyst is 1 part of stannous octoate.
In the present embodiment, heat stabilizer is 0.8 part of triphenyl phosphite.
In the present embodiment, solvent is 5 parts of toluene, 35 parts of dimethylbenzene.
Embodiment 8
A kind of preparation method of silicone modified polyester resin, the described method comprises the following steps:
(1) 50 parts of multicomponent organic acids, 36 parts of polyalcohols, 0.3 part of catalyst and 22 parts of dimethylbenzene are mixed, is protected in nitrogen
It is warming up at 170 DEG C under shield with 4 DEG C/min and reacts 50min, 0.3 part of heat stabilizer is added with 1 DEG C/min and is warming up to 230 DEG C of reactions
50min, while water is steamed, 2 parts of polyalcohols and 3 parts of dimethylbenzene are added after being cooled to 180 DEG C, are warming up to 220 DEG C instead with 1 DEG C/min
It answers, 5 parts of toluene is added after reaction and obtain polyester resin solution；
(2) 68 parts, 20 parts silicone intermediates of polyester resin solution for obtaining step (1), 0.1 part of heat stabilizer, 0.5
Part catalyst and 6 parts of dimethylbenzene mixing, are warming up to 170 DEG C of reaction 60min, then be warming up to 190 DEG C of reactions under nitrogen protection
60min, then 210 DEG C of reactions are warming up to, reaction to reaction stops water outlet, obtains silicone modified polyester resin.
In the present embodiment, multicomponent organic acid is 50 parts of adipic acid.
In the present embodiment, polyalcohol is 38 parts of trimethylolpropane.
In the present embodiment, silicone intermediate is 20 parts of road DOW CORNING Z-6018.
In the present embodiment, catalyst is 0.8 part of stannous octoate.
In the present embodiment, heat stabilizer is 0.4 part of triphenyl phosphite.
In the present embodiment, solvent is 5 parts of toluene, 31 parts of dimethylbenzene.
Embodiment 9
A kind of preparation method of silicone modified polyester resin, the method use road DOW CORNING in addition to silicone intermediate
Other than 3288, other conditions are same as Example 1.
Embodiment 10
A kind of preparation method of silicone modified polyester resin, the method use RSN-6018 in addition to silicone intermediate
In addition, other conditions are same as Example 1.
Comparative example 1
A kind of preparation method of silicone modified polyester resin, the method joined 5 especially in addition to silicone intermediate,
Other conditions are same as Example 1.
Comparative example 2
A kind of preparation method of silicone modified polyester resin, the method joined 50 parts in addition to silicone intermediate
Outside, other conditions are same as Example 1.
Comparative example 3
A kind of preparation method of silicone modified polyester resin, the method directly react temperature in third in addition to step (1)
The lower reaction of degree is outer, and other conditions are same as Example 1.
Comparative example 4
A kind of preparation method of silicone modified polyester resin, the method is in addition to step (2) is directly in the 6th reaction temperature
The lower reaction of degree is outer, and other conditions are same as Example 1.
The silicone modified polyester resin that embodiment 1-10 and comparative example 1-4 are prepared carry out adhesive force, hardness,
Solid content, boiling test, soaked test, acid proof test, alkaline-resisting test, resistance to Thermal test, RCA test and surface tension test.
Specific testing standard or method are as shown in table 1.
Table 1
The above test result is as shown in table 2.
Table 2
According to table 2 as can be seen that the adhesive force for the organic-silicon-modified resin that embodiment 1-8 is prepared is 0 grade, have good
Good adhesion property, hardness is up to 3H, while acid and alkali-resistance and heat resistance are good, and wear-resisting property is good, and RCA is tested up to 50 times.
Embodiment 9 and embodiment 10 use other silicone intermediates, the silicone modified polyester resin being prepared it is heat-resisting
Performance decline, RCA test are 38 times and 32 times, and wear-resisting property is deteriorated.The additional amount of the silicone intermediate of comparative example 1 and 2 is 12
Except~25 parts, the hardness for the silicone modified polyester resin being prepared is caused to drop to H, and RCA test for 43 times and
35 times, wear-resisting property is deteriorated.Comparative example 3 and 4 does not carry out heating distribution reaction in preparation method, but directly reacts, and causes
The acid and alkali-resistance and waterproof performance for the silicone modified polyester resin being prepared decline, and RCA test is 45 times and 41 times, wearability
It can be declined.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (18)
1. a kind of silicone modified polyester resin, which is characterized in that the resin includes following components in parts by weight:
Wherein, the silicone intermediate includes DOW CORNING 3037 and/or DOW CORNING Z-6018；
The preparation method of the silicone modified polyester resin the following steps are included:
(1) multicomponent organic acid, polyalcohol, catalyst and solvent are mixed, is warming up at 160~180 DEG C under a shielding gas
Reaction is added heat stabilizer and is warming up to 210~250 DEG C of reactions, polynary alcohol and solvent is added after being cooled to 160~200 DEG C, heats up
It is reacted to 210~240 DEG C, obtains polyester resin solution；
(2) polyester resin solution, silicone intermediate, heat stabilizer, catalyst and the solvent mixing obtained step (1),
It is warming up to 160~180 DEG C of reactions under a shielding gas, then is warming up to 185~195 DEG C of reactions, then is warming up to 200~220 DEG C instead
It answers, obtains silicone modified polyester resin；
Wherein, the mass ratio for the polyalcohol that the polyalcohol being added after step (1) described cooling is added before reacting with step (1) is 1:
(16~23)；The solvent being added after step (1) described cooling reacted with step (1) before be added solvent mass ratio be 1:(5~
10)；The mass ratio for the heat stabilizer that the heat stabilizer and step (1) that step (2) is added are added is 1:(1~3)；Step (2) adds
The mass ratio for the catalyst that the catalyst entered and step (1) are added is (1~2.5): 1；The solvent and step that step (2) is added
(1) mass ratio for the solvent being added is 1:(3.5~9).
2. silicone modified polyester resin according to claim 1, which is characterized in that the multicomponent organic acid includes to benzene
Any one in dioctyl phthalate, phthalic acid or adipic acid or at least two combination.
3. silicone modified polyester resin according to claim 1, which is characterized in that the polyalcohol includes new penta 2
Any one in alcohol, diglycol or trimethylolpropane or at least two combination.
4. silicone modified polyester resin according to claim 1, which is characterized in that the catalyst includes that octanoic acid is sub-
Tin.
5. silicone modified polyester resin according to claim 1, which is characterized in that the heat stabilizer includes phosphorous acid
Triphenylmethyl methacrylate.
6. silicone modified polyester resin according to claim 1, which is characterized in that the solvent include toluene and/or
Dimethylbenzene.
7. a kind of preparation method of resin described in any one of claims 1-6, which is characterized in that the preparation method include with
Lower step:
(1) multicomponent organic acid, polyalcohol, catalyst and solvent are mixed, is warming up at 160~180 DEG C under a shielding gas
Reaction is added heat stabilizer and is warming up to 210~250 DEG C of reactions, polynary alcohol and solvent is added after being cooled to 160~200 DEG C, heats up
It is reacted to 210~240 DEG C, obtains polyester resin solution；
(2) polyester resin solution, silicone intermediate, heat stabilizer, catalyst and the solvent mixing obtained step (1),
It is warming up to 160~180 DEG C of reactions under a shielding gas, then is warming up to 185~195 DEG C of reactions, then is warming up to 200~220 DEG C instead
It answers, obtains silicone modified polyester resin.
8. preparation method according to claim 7, which is characterized in that the time of (1) 160~180 DEG C of step reaction is 40
~60min.
9. preparation method according to claim 7, which is characterized in that step (1) is warming up to 160~180 DEG C of heating speed
Rate is 4~6 DEG C/min.
10. preparation method according to claim 7, which is characterized in that step (1) described protective gas includes nitrogen, helium
Any one in gas or argon gas or at least two combination.
11. preparation method according to claim 7, which is characterized in that the time of (1) 210~250 DEG C of step reaction is 40
~60min.
12. preparation method according to claim 7, which is characterized in that step (1) is warming up to 210~250 DEG C of heating speed
Rate is 0.5~2 DEG C/min.
13. preparation method according to claim 7, which is characterized in that same during (1) 210~250 DEG C of step reaction
When steam water.
14. preparation method according to claim 7, which is characterized in that step (1) is warming up to the heating at 210~240 DEG C
Rate is 0.3~2 DEG C/min.
15. preparation method according to claim 7, which is characterized in that reaction time of the step (2) at 160~180 DEG C
For 45~75min.
16. preparation method according to claim 7, which is characterized in that step (2) is warming up under 185~195 DEG C of reactions
Reaction time is 45~75min.
17. preparation method according to claim 7, which is characterized in that step (2) is warming up to the reaction at 200~220 DEG C
Stop water outlet to reaction.
18. according to the described in any item preparation methods of claim 7-17, which is characterized in that the described method comprises the following steps:
(1) multicomponent organic acid, polyalcohol, catalyst and solvent are mixed, is warming up at 160~180 DEG C under a shielding gas
40~60min is reacted, heat stabilizer is added and is warming up to 210~250 DEG C of 40~60min of reaction, while steaming water, is cooled to 160
Polynary alcohol and solvent is added after~200 DEG C, is warming up to 210~240 DEG C of reactions, obtains polyester resin solution；
(2) polyester resin solution, silicone intermediate, heat stabilizer, catalyst and the solvent mixing obtained step (1),
It is warming up to 160~180 DEG C of 45~75min of reaction under a shielding gas, then is warming up to 185~195 DEG C of 45~75min of reaction, then
200~220 DEG C of reactions are warming up to, reaction to reaction stops water outlet, obtains silicone modified polyester resin.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103304795A (en) * | 2013-06-17 | 2013-09-18 | 中国纺织科学研究院 | Organosilicone copolyester |
| CN105482089A (en) * | 2015-12-26 | 2016-04-13 | 杭州吉华高分子材料股份有限公司 | Water-soluble organic silicone modified polyester resin as well as preparation method and application thereof |
| CN106220838A (en) * | 2016-08-29 | 2016-12-14 | 杭州吉华高分子材料股份有限公司 | A kind of hydrophobic heat-resisting silicone modified polyester resin and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304795A (en) * | 2013-06-17 | 2013-09-18 | 中国纺织科学研究院 | Organosilicone copolyester |
| CN105482089A (en) * | 2015-12-26 | 2016-04-13 | 杭州吉华高分子材料股份有限公司 | Water-soluble organic silicone modified polyester resin as well as preparation method and application thereof |
| CN106220838A (en) * | 2016-08-29 | 2016-12-14 | 杭州吉华高分子材料股份有限公司 | A kind of hydrophobic heat-resisting silicone modified polyester resin and preparation method thereof |
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