CN103897197A - Preparation method of organic silicon-modified polyester epoxy resin - Google Patents
Preparation method of organic silicon-modified polyester epoxy resin Download PDFInfo
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- CN103897197A CN103897197A CN201210585860.7A CN201210585860A CN103897197A CN 103897197 A CN103897197 A CN 103897197A CN 201210585860 A CN201210585860 A CN 201210585860A CN 103897197 A CN103897197 A CN 103897197A
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Abstract
The invention provides a preparation method of organic silicon-modified polyester epoxy resin. The preparation method comprises the following steps: (1) providing a mixture of the following components: a polyester reactant, polysiloxane, epoxy resin and a selectable polymerization reaction catalyst, wherein the hydroxy content of the polyester reactant is 8-17.1%, the epoxy resin contains hydroxide radicals and epoxy functional groups, the weight ratio of polysiloxane to polyester reactant is (30-90):(10-70), the weight of the epoxy resin is equal to 5-15% of the total weight of polysiloxane and polyester reactant, and the weight of the polymerization reaction catalyst is equal to 0-0.5% of the total weight of polysiloxane and polyester reactant; (2) reacting for 3-4 hours by virtue of the mixture at 120-170 DEG C, so as to obtain the organic silicon-modified polyester epoxy resin. The invention further provides the organic silicon-modified polyester epoxy resin and a product of the organic silicon-modified polyester epoxy resin.
Description
Technical field
The present invention relates to a kind of preparation method of resin, especially the preparation method of organosilicon modified polyester epoxy resin.
Background technology
Silicone modified polyester resin is a class novel high polymer material, is widely used in paint field, especially as metal protective coating and decorative paint.From molecular structure, it has the two-fold advantage of silicone resin and vibrin, has excellent thermotolerance, winter hardiness, weathering resistance, electric insulating quality and mechanical property.Epoxy resin has good physics, chemical property, and it has excellent bonding strength to the surface of metal and non-metallic material, and shrinking percentage is little, good stability of the dimension, and chemical resistance is good.If epoxy resin is combined and is applied in coating with organosilicon polyester, can improve adherence and the corrosion resistance nature of coating.
CN101307220A discloses a kind of organosilicon modified polyester electronic packaging material, it contains the composition such as epoxy resin, organosilicon modified polyester in forming, solidifying agent using organosilicon modified polyester as epoxy resin, make by pre-mixing, melting mixing, there is good water tolerance and electrical insulation capability.CN101885944A discloses a kind of organic silicon polyester resin coating, is dual-component coating, wherein in component A, contains modified organic silicon vibrin, and this modified organic silicon vibrin is obtained by organic silicon polyester resin and epoxy resin and other solvent; After being mixed by the weight proportion of 1: 1, component A and component B obtain organic silicon polyester resin coating.Have that toxicity is low, construction application is convenient, film is tough and tensile, wear-resisting, cohesive force is strong, permeability resistance is good and etch resistant properties is excellent.
Above-mentioned disclosed technical scheme is all to adopt the method that organosilicon polyester is mixed with epoxy resin to make product, and products obtained therefrom exists the shortcoming of xanthochromia while use under hot conditions, cannot be applicable in the field of cooking utensil.Therefore, this area is in the urgent need to developing a kind of organosilicon polyester epoxy resin and preparation method who overcomes high temperature xanthochromia again can be acidproof.
Summary of the invention
The first object of the present invention is to obtain a kind of organosilicon polyester epoxy resin that overcomes high temperature xanthochromia again can be acidproof.
The second object of the present invention is to obtain a kind of organosilicon polyester epoxy resin preparation method who overcomes high temperature xanthochromia again can be acidproof.
A first aspect of the present invention provides a kind of preparation method of organosilicon modified polyester epoxy resin, and it comprises the following steps:
(a) provide the mixture of following component:
The pet reaction thing of hydroxy radical content 8～17.1%;
Polysiloxane;
The epoxy resin of hydroxyl and epoxide functional groups;
Optional polymerisation catalysts;
Wherein, the weight ratio of described polysiloxane and pet reaction thing is (30～90): (10～70);
The weight of the epoxy resin of described hydroxyl and epoxide functional groups account for described polysiloxane and pet reaction thing gross weight 5～15%;
Described polymerisation catalysts account for described polysiloxane and pet reaction thing gross weight 0～0.5%
(b) described mixture reacts 3～4 hours under the temperature of reaction of 120～170 DEG C, obtains organosilicon modified polyester epoxy resin of the present invention.
In a specific embodiment of the present invention, the polyester of described hydroxy radical content 8～17.1% obtains in accordance with the following steps:
According to being that 1.65～3:1 adds polyvalent alcohol and polyprotonic acid by hydroxyl equivalent and carboxyl equivalent mol ratio, under the temperature of reaction of 180～230 DEG C, react to acid number for lower than 10mgKOH/g, obtain the pet reaction thing of hydroxy radical content 8～17.1%.
In a specific embodiment of the present invention, described polyvalent alcohol is TriMethylolPropane(TMP) and/or trimethylolethane; Or
Described polyprotonic acid is terephthalic acid and/or m-phthalic acid.
In a specific embodiment of the present invention, described polysiloxane general formula is: R
1 a(R
2o)
bsiO
(4-a-b)/2,
Wherein,
R
1be selected from aromatic base, alkyl or thiazolinyl;
R
2be selected from H or alkyl; As described R
2while being selected from H, described R
2o is silicon hydroxyl, and the described polysiloxane silicon hydroxyl that contains 2～7wt%; As described R
2while being selected from alkyl, described R
2o is silicon alkoxyl group, and the described polysiloxane silicon alkoxyl group that contains 13～20wt%;
In formula, a+b=1～3, and b > 0, and be positive integer; Described polysiloxane contains at least one or the multiple repeating unit with following formula:
When a+b=1, contain T unit: R
1 a(R
2o)
bsiO
3/2;
When a+b=2, contain D unit: R
1 a(R
2o)
bsiO
2/2;
When a+b=3, contain M unit: R
1 a(R
2o)
bsiO
1/2;
Taking the total mole number of described polysiloxane as benchmark, described polysiloxane comprises T unit, the D unit of 0～15mol% and the M unit of 0～20mol% of 30～100mol%;
The weight-average molecular weight of described polysiloxane is 800～4000.
In an embodiment, the silicon hydroxyl (R that described polysiloxane contains 2～6wt%
2for H) or the silicon alkoxyl group (R of 14～16wt%
2for alkyl).
In an embodiment, described polysiloxane comprises T unit, the D unit of 0～10mol% and the M unit of 0～10mol% of 75～100mol%.
In an embodiment, the silicon hydroxyl (R that described polysiloxane contains 2～6wt%
2for H) or the silicon alkoxyl group (R of 14～16wt%
2for alkyl).
In an embodiment, described polysiloxane comprises T unit, the D unit of 0～10mol% and the M unit of 0～10mol% of 75～100mol%.
In an embodiment, described polysiloxane comprises the T unit of 85～95mol% and the D unit of 5～15mol%.
In an embodiment, described R
1the preferred phenyl of aromatic base.
In an embodiment, described R
1alkyl is selected from methyl, ethyl or propyl group.
In an embodiment, described R
1thiazolinyl is selected from vinyl.
In an embodiment, described R
2alkyl is selected from methyl, ethyl, propyl group or butyl.
In an embodiment, described polysiloxane is phenyl polysiloxane or methyl phenyl silicone.
In an embodiment, the silicon hydroxyl (R that described polysiloxane contains 2～6wt%
2for H) or the silicon alkoxyl group (R of 14～16wt%
2for alkyl).
In an embodiment, described polysiloxane comprises T unit, the D unit of 0～10mol% and the M unit of 0～10mol% of 75～100mol%.
In a specific embodiment of the present invention, described hydroxyl and the epoxy resin of epoxide functional groups are bisphenol A type epoxy resin, and epoxy equivalent (weight) is 450～1000.
In a specific embodiment of the present invention, described hydroxyl and the epoxy resin of epoxide functional groups by bisphenol f type epoxy resin and Bisphenol F or bisphenol S in molar ratio 2 ± 0.5:1 react and make for 3 ± 1 hours at 150 ± 30 DEG C, epoxy equivalent (weight) is 450～1000.
In a specific embodiment of the present invention, described polymerisation catalysts is titanate ester catalyzer.
The organosilicon modified polyester epoxy resin that a second aspect of the present invention provides a kind of method as described in the present invention to make.
Embodiment
The inventor, through extensive and deep research, by improving preparation method, has obtained a kind of organic silicon polyester resin and preparation method who overcomes high temperature xanthochromia again can be acidproof.Complete on this basis the present invention.
In the present invention, term " contains " or " comprising " represents that various compositions can be applied in mixture of the present invention or composition together.Therefore, term " mainly by ... composition " and " by ... form " be included in that term " contains " or in " comprising ".
Below describe in detail to various aspects of the present invention:
The preparation method of organosilicon modified polyester epoxy resin
A first aspect of the present invention provides a kind of preparation method of organosilicon modified polyester epoxy resin, and it comprises the following steps:
(a) provide the mixture of following component:
The pet reaction thing of hydroxy radical content 8～17.1%;
Polysiloxane;
The epoxy resin of hydroxyl and epoxide functional groups;
Optional polymerisation catalysts;
Wherein, the weight ratio of described polysiloxane and pet reaction thing is (30～90): (10～70);
The weight of the epoxy resin of described hydroxyl and epoxide functional groups account for described polysiloxane and pet reaction thing gross weight 5～15%;
Described polymerisation catalysts account for described polysiloxane and pet reaction thing gross weight 0～0.5%
(b) described mixture reacts 3～4 hours under the temperature of reaction of 120～170 DEG C, obtains organosilicon modified polyester epoxy resin of the present invention.
Inventor's discovery, when adopting after described component mixture reaction, the organosilicon modified polyester epoxy resin obtaining can overcome high temperature xanthochromia again can be acidproof.
The order of addition of described step (a) is best in the following manner:
Polysiloxane is mixed 30～90:10～70 in mass ratio with the pet reaction thing of hydroxy radical content 8～17.1%, then add the polymerisation catalysts that accounts for polysiloxane and the hydroxyl of pet reaction thing total mass 5～15% and the epoxy resin of epoxide functional groups and account for all reactant total masses 0～0.5%, under the temperature of reaction of 120～170 DEG C, react 3～4 hours, obtain organosilicon modified polyester epoxy resin of the present invention.
In a specific embodiment of the present invention, the polyester of described hydroxy radical content 8～17.1% obtains in accordance with the following steps:
According to being that 1.65～3:1 adds polyvalent alcohol and polyprotonic acid by hydroxyl equivalent and carboxyl equivalent mol ratio, under the temperature of reaction of 180～230 DEG C, react to acid number for lower than 10mgKOH/g, obtain the pet reaction thing of hydroxy radical content 8～17.1%.
Contriver is controlled at the acid number of reaction system lower than 10mgKOH/g, thereby controls described polyreaction and obtain " the pet reaction thing of hydroxy radical content 8～17.1% ".
The pet reaction thing of described hydroxy radical content 8～17.1% also can be obtained by other conventional polyester reactions, but reaction system need to be controlled at the acid number of reaction system lower than 10mgKOH/g.
Described reaction system can also add appropriate solvent.Described solvent should be inert solvent, reaction of the present invention is not exerted an influence, for example appropriate 1-Methoxy-2-propyl acetate (PMA).
In a specific embodiment of the present invention, described polyvalent alcohol is TriMethylolPropane(TMP) and/or trimethylolethane; Or
Described polyprotonic acid is terephthalic acid and/or m-phthalic acid.
In a specific embodiment of the present invention, described polysiloxane general formula is: R
1 a(R
2o)
bsiO
(4-a-b)/2,
Wherein,
R
1be selected from aromatic base, alkyl or thiazolinyl;
R
2be selected from H or alkyl; As described R
2while being selected from H, described R
2o is silicon hydroxyl, and the described polysiloxane silicon hydroxyl that contains 2～7wt%; As described R
2while being selected from alkyl, described R
2o is silicon alkoxyl group, and the described polysiloxane silicon alkoxyl group that contains 13～20wt%;
In formula, a+b=1～3, and b > 0, and be positive integer; Described polysiloxane contains at least one or the multiple repeating unit with following formula:
When a+b=1, contain T unit: R
1 a(R
2o)
bsiO
3/2;
When a+b=2, contain D unit: R
1 a(R
2o)
bsiO
2/2;
When a+b=3, contain M unit: R
1 a(R
2o)
bsiO
1/2;
Taking the total mole number of described polysiloxane as benchmark, described polysiloxane comprises T unit, the D unit of 0～15mol% and the M unit of 0～20mol% of 30～100mol%;
The weight-average molecular weight of described polysiloxane is 800～4000.
In an embodiment, the silicon hydroxyl (R that described polysiloxane contains 2～6wt%
2for H) or the silicon alkoxyl group (R of 14～16wt%
2for alkyl).
In an embodiment, described polysiloxane comprises T unit, the D unit of 0～10mol% and the M unit of 0～10mol% of 75～100mol%.
In an embodiment, described polysiloxane comprises the T unit of 85～95mol% and the D unit of 5～15mol%.
In an embodiment, the silicon hydroxyl (R that described polysiloxane contains 2～6wt%
2for H) or the silicon alkoxyl group (R of 14～16wt%
2for alkyl).
In an embodiment, described polysiloxane comprises T unit, the D unit of 0～10mol% and the M unit of 0～10mol% of 75～100mol%.
In an embodiment, described R
1the preferred phenyl of aromatic base.
In an embodiment, described R
1alkyl is selected from methyl, ethyl or propyl group.
In an embodiment, described R
1thiazolinyl is selected from vinyl.
In an embodiment, described R
2alkyl is selected from methyl, ethyl, propyl group or butyl.
In an embodiment, described polysiloxane is phenyl polysiloxane or methyl phenyl silicone.
In an embodiment, the silicon hydroxyl (R that described polysiloxane contains 2～6wt%
2for H) or the silicon alkoxyl group (R of 14～16wt%
2for alkyl).
In an embodiment, described polysiloxane comprises T unit, the D unit of 0～10mol% and the M unit of 0～10mol% of 75～100mol%.
In a specific embodiment of the present invention, described hydroxyl and the epoxy resin of epoxide functional groups are bisphenol A type epoxy resin, and epoxy equivalent (weight) is 450～1000.
In a specific embodiment of the present invention, described hydroxyl and the epoxy resin of epoxide functional groups by bisphenol f type epoxy resin and Bisphenol F or bisphenol S in molar ratio 2 ± 0.5:1 react and make for 3 ± 1 hours at 150 ± 30 DEG C, epoxy equivalent (weight) is 450～1000.
In a specific embodiment of the present invention, described polymerisation catalysts is titanate ester catalyzer.
Described titanate ester catalyzer can optionally add.The phthalate catalyzer adopting is not specifically limited, only otherwise goal of the invention of the present invention is produced to restriction.
Concrete includes but not limited to: phthalate catalyzer is tetrabutyl titanate or isopropyl titanate.
Organosilicon modified polyester epoxy resin and goods thereof
The organosilicon modified polyester epoxy resin that a second aspect of the present invention provides a kind of method as described in the present invention to make.
The preferred embodiments of the present invention
The object of the present invention is to provide a kind of preparation method of organosilicon modified polyester epoxy resin, preparation technology of the present invention is simple, and side reaction is few, and productive rate is high; Gained organosilicon epoxy polyester has excellent heat-resisting, capable of resisting high-temperature yellowing performance and acid resistance.
Another object of the present invention is to provide a kind of organosilicon modified polyester epoxy resin, and gained organosilicon epoxy polyester has excellent heat-resisting, capable of resisting high-temperature yellowing performance and acid resistance.
The preparation method of organosilicon modified polyester epoxy resin of the present invention is as follows:
1) in reaction vessel, be that 1.65～3:1 adds polyvalent alcohol and polyprotonic acid by hydroxyl equivalent and carboxyl equivalent mol ratio, under the temperature of reaction of 180～230 DEG C, react to acid number for lower than 10mgKOH/g, obtain the pet reaction thing of hydroxy radical content 8～17.1%;
2) by polysiloxane and step 1) the pet reaction thing that obtains mixes 30～90:10～70 in mass ratio, then add the polymerisation catalysts that accounts for polysiloxane and the hydroxyl of pet reaction thing total mass 5～15% and the epoxy resin of epoxide functional groups and account for all reactant total masses 0～0.5%, under the temperature of reaction of 120～170 DEG C, react 3～4 hours, obtain organosilicon modified polyester epoxy resin of the present invention.
Described polyvalent alcohol is TriMethylolPropane(TMP) and/or trimethylolethane, can add on a small quantity ethyl butyl propanediol, neopentyl glycol, butyleneglycol, propylene glycol.
Described polyprotonic acid is terephthalic acid and/or m-phthalic acid, can add on a small quantity trimellitic acid 1,2-anhydride, succinic acid, hexanodioic acid.
Described polysiloxane general formula is: R
1 a(R
2o)
bsiO
(4-a-b)/2, wherein, R
1preferably from aromatic base if phenyl, alkyl are if methyl, ethyl or propyl group or thiazolinyl are as vinyl; R
2preferably from H or alkyl as methyl, ethyl, propyl group or butyl; Silicon hydroxyl (the R that described polysiloxane contains 2～7wt%
2for H) or the silicon alkoxyl group (R of 13～20wt%
2for alkyl), preferably contain the silicon hydroxyl (R of 2～6wt%
2for H) or the silicon alkoxyl group (R of 14～16wt%
2for alkyl).
In formula, a+b=1～3, and b > 0; Polysiloxane contains at least one or the multiple repeating unit with following formula:
When a+b=1, T unit: R
1 a(R
2o)
bsiO
3/2;
When a+b=2, D unit: R
1 a(R
2o)
bsiO
2/2;
When a+b=3, M unit: R
1 a(R
2o)
bsiO
1/2.
Taking the total mole number of described polysiloxane as benchmark, described polysiloxane comprises T unit, the D unit of 0～15mol% and the M unit of 0～20mol% of 30～100mol%; Preferably include T unit, the D unit of 0～10mol% and the M unit of 0～10mol% of 75～100mol%.
The weight-average molecular weight of described polysiloxane is 800～4000.Described polysiloxane is phenyl polysiloxane, methyl phenyl silicone more preferably.
Described polymerisation catalysts is titanate ester catalyzer, is preferably tetrabutyl titanate or isopropyl titanate.
Described hydroxyl and the epoxy resin of epoxide functional groups are bisphenol A type epoxy resin, and epoxy equivalent (weight) is 450～1000.
Described hydroxyl and the epoxy resin of epoxide functional groups by bisphenol f type epoxy resin and Bisphenol F or bisphenol S in molar ratio 2:1 react and make for 3 hours at 150 DEG C, epoxy equivalent (weight) is 450～1000.
Preparation technology of the present invention is simple, and gained organosilicon modified polyester epoxy resin has heat-resisting, anti-yellowing property significantly, and good acid resistance.
As no specific instructions, various raw material of the present invention all can obtain by commercially available; Or prepare according to the ordinary method of this area.Unless otherwise defined or described herein, the familiar same meaning of all specialties used herein and scientific words and those skilled in the art.In addition any method similar or impartial to described content and material all can be applicable in the inventive method.
Above-mentioned synthetic method is the synthetic route of part of compounds of the present invention, according to above-mentioned example, those skilled in the art can synthesize other compounds of the present invention by adjusting diverse ways, or those skilled in the art can synthesize compound of the present invention according to existing known technology.
Other aspects of the present invention, due to disclosure herein, are apparent to those skilled in the art.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.The experimental technique of unreceipted actual conditions in the following example, measures according to national standard conventionally.If there is no corresponding national standard, carry out according to general international standard, normal condition or the condition of advising according to manufacturer.Unless otherwise indicated, otherwise all umbers are weight part, and all per-cents are weight percentage, and described polymericular weight is number-average molecular weight.
Unless otherwise defined or described herein, the familiar same meaning of all specialties used herein and scientific words and those skilled in the art.In addition any method similar or impartial to described content and material all can be applicable in the inventive method.
Nomenclature of drug and source that the present invention is used are listed below, but are not limited only to listed medicine:
(1) polysiloxane:
The DC-217 that Dow corning company sells, purified petroleum benzin based polysiloxane, R
1be phenyl and silicon hydroxyl (R
2for H) content is 6.0wt%;
The Silres IC678 that Wa Ke company of Germany sells, purified petroleum benzin based polysiloxane, R
1be phenyl and silicon methoxyl group (R
2for methyl) content is 14.0wt%;
The Silres REN168 that Wa Ke company of Germany sells, methyl phenyl silicone, phenyl and methyl (R
1) mol ratio be 1.1:1.0, and silicon hydroxyl (R
2for H) content is 4.0～5.0wt%.
(2) bisphenol A type epoxy resin:
The EPIKOTE that Momentive Specialty Chemicals Inc. sells
tMresin1001, epoxy equivalent (weight) 450～500, solid; EPIKOTE
tMresin1004, epoxy equivalent (weight) 806～909, solid;
The NPES-904 that Nan Ya Plastics company sells, epoxy equivalent (weight) 780～850, solid.
(3) hydroxyl bisphenol f type epoxy resin:
NPEF-170-a: by 2mol (340g) bisphenol f type epoxy resin (NPEF-170 that Nan Ya Plastics company sells, epoxy equivalent (weight) 160～180, liquid) react and make for 3 hours at 150 DEG C with 1mol (200g) Bisphenol F, epoxy equivalent (weight) is 600.
NPEF-170-b: by 2mol (340g) bisphenol f type epoxy resin (NPEF-170 that Nan Ya Plastics company sells, epoxy equivalent (weight) 160～180, liquid) react and make for 3 hours at 150 DEG C with 1mol (250g) bisphenol S, epoxy equivalent (weight) is 650.
In order to understand feature of the present invention, now enumerate following embodiment with the person of ordinary skill in the art is more clear that.
Embodiment 1
In the reaction vessel that is connected with nitrogen, add 268g TriMethylolPropane(TMP), 166g m-phthalic acid, isothermal reaction after being heated to 220 DEG C, dehydration, below acid number drops to 10mgKOH/g time, be cooled to 140 DEG C, add appropriate 1-Methoxy-2-propyl acetate (PMA), make solid content and be 75% pet reaction thing, hydroxy radical content 17.1%;
Get the pet reaction thing that the above-mentioned solid content of 40g is 75% and join in reaction vessel, be heated to after 100 DEG C, add 70g polysiloxane DC-217,8g bisphenol A type epoxy resin EPIKOTE
tMresin1001, the PMA that the tetrabutyl titanate of 0.5g is made catalyzer and 35g is solvent, continues to be warmed up to approximately 120 DEG C, dehydration, isothermal reaction 3～4 hours, cooling, then add propyl carbinol, dimethylbenzene equal solvent to stir 30 minutes, adjust resin viscosity 500～1500cps, solid part 60%.
Embodiment 2
In the reaction vessel that is connected with nitrogen, add 134g TriMethylolPropane(TMP), 60g trimethylolethane, 166g terephthalic acid, isothermal reaction after being heated to 230 DEG C, dehydration, below acid number drops to 10mgKOH/g time, be cooled to 140 DEG C, add appropriate 1-Methoxy-2-propyl acetate (PMA), make solid content and be 75% pet reaction thing, hydroxy radical content 13.1%;
Get the pet reaction thing that the above-mentioned solid content of 60g is 75% and join in reaction vessel, be heated to after 100 DEG C, add 55g polysiloxane Silres REN168,5g bisphenol A type epoxy resin EPIKOTE
tMresin1004, the PMA that the isopropyl titanate of 0.1g is made catalyzer and 30g is solvent, continues to be warmed up to approximately 140 DEG C, dehydration, isothermal reaction 3～4 hours, cooling, then add propyl carbinol, dimethylbenzene equal solvent to stir 30 minutes, adjust resin viscosity 500～1500cps, solid part 60%.
Embodiment 3
In the reaction vessel that is connected with nitrogen, add 134g TriMethylolPropane(TMP), 20.8g neopentyl glycol, 169.8g m-phthalic acid, isothermal reaction after being heated to 180 DEG C, dehydration, below acid number drops to 10mgKOH/g time, be cooled to 140 DEG C, add appropriate 1-Methoxy-2-propyl acetate (PMA), make solid content and be 75% pet reaction thing, hydroxy radical content 8.0%;
Getting the pet reaction thing that the above-mentioned solid content of 100g is 75% joins in reaction vessel, be heated to after 100 DEG C, add 25g polysiloxane Silres IC678,10g bisphenol A type epoxy resin NPES-904, and the PMA of 20g is solvent, continue to be warmed up to approximately 150 DEG C, separating methanol, isothermal reaction 3～4 hours, cooling, then add propyl carbinol, dimethylbenzene equal solvent to stir 30 minutes, adjust resin viscosity 500～1500cps, solid part 60%.
Embodiment 4
In the reaction vessel that is connected with nitrogen, add 40.2g TriMethylolPropane(TMP), 120g trimethylolethane, 83g terephthalic acid and 83g m-phthalic acid, isothermal reaction after being heated to 200 DEG C, dehydration, below acid number drops to 10mgKOH/g time, be cooled to 140 DEG C, add appropriate 1-Methoxy-2-propyl acetate (PMA), make solid content and be 75% pet reaction thing, hydroxy radical content 11.1%;
Getting the pet reaction thing that the above-mentioned solid content of 80g is 75% joins in reaction vessel, be heated to after 100 DEG C, add 40g polysiloxane DC-217,15g bisphenol f type epoxy resin NPEF-170-a, the PMA that the tetrabutyl titanate of 0.3g is made catalyzer and 28g is solvent, continue to be warmed up to approximately 140 DEG C, dehydration, isothermal reaction 3～4 hours, cooling, then add propyl carbinol, dimethylbenzene equal solvent to stir 30 minutes, adjust resin viscosity 500～1500cps, solid part 60%.
Embodiment 5
In the reaction vessel that is connected with nitrogen, add 240g trimethylolethane, 166g m-phthalic acid and 19.2g trimellitic acid 1,2-anhydride, isothermal reaction after being heated to 220 DEG C, dehydration, below acid number drops to 10mgKOH/g time, be cooled to 140 DEG C, add appropriate 1-Methoxy-2-propyl acetate (PMA), make solid content and be 75% pet reaction thing, hydroxy radical content 16.4%;
Getting the pet reaction thing that the above-mentioned solid content of 120g is 75% joins in reaction vessel, be heated to after 100 DEG C, add 10g polysiloxane DC-217,6g bisphenol f type epoxy resin NPEF-170-b, the PMA that the tetrabutyl titanate of 0.1g is made catalyzer and 20g is solvent, continue to be warmed up to approximately 170 DEG C, dehydration, isothermal reaction 3～4 hours, cooling, then add propyl carbinol, dimethylbenzene equal solvent to stir 30 minutes, adjust resin viscosity 500～1500cps, solid part 60%.
Comparative example 1
In the reaction vessel that is connected with nitrogen, add 268g TriMethylolPropane(TMP), 166g m-phthalic acid, isothermal reaction after being heated to 220 DEG C, dehydration, below acid number drops to 10mgKOH/g time, be cooled to 140 DEG C, add appropriate 1-Methoxy-2-propyl acetate (PMA), make solid content and be 75% pet reaction thing, hydroxy radical content 17.1%;
Getting the pet reaction thing that the above-mentioned solid content of 40g is 75% joins in reaction vessel, be heated to after 100 DEG C, add 70g polysiloxane DC-217, the PMA that the tetrabutyl titanate of 0.5g is made catalyzer and 30g is solvent, continues to be warmed up to approximately 120 DEG C, dehydration, isothermal reaction 3～4 hours, cooling, then adds propyl carbinol, dimethylbenzene equal solvent to stir 30 minutes, adjusts resin viscosity 500～1500cps, solid part 60%.
Comparative example 2
In the reaction vessel that is connected with nitrogen, add 134g TriMethylolPropane(TMP), 60g trimethylolethane, 166g terephthalic acid, isothermal reaction after being heated to 230 DEG C, dehydration, below acid number drops to 10mgKOH/g time, be cooled to 140 DEG C, add appropriate 1-Methoxy-2-propyl acetate (PMA), make solid content and be 75% pet reaction thing, hydroxy radical content 13.1%;
Getting the pet reaction thing that the above-mentioned solid content of 60g is 75% joins in reaction vessel, be heated to after 100 DEG C, add 55g polysiloxane Silres REN168, the PMA that the isopropyl titanate of 0.1g is made catalyzer and 30g is solvent, continue to be warmed up to approximately 140 DEG C, dehydration, isothermal reaction 3～4 hours, cooling, then adds 5g bisphenol A type epoxy resin EPIKOTE
tMresin1004, then add propyl carbinol, dimethylbenzene equal solvent to stir 30 minutes, adjust resin viscosity 500～1500cps, solid part 60%.
Comparative example 3
In the reaction vessel that is connected with nitrogen, add 40.2g TriMethylolPropane(TMP), 120g trimethylolethane, 83g terephthalic acid and 83g m-phthalic acid, isothermal reaction after being heated to 200 DEG C, dehydration, below acid number drops to 10mgKOH/g time, be cooled to 140 DEG C, add appropriate 1-Methoxy-2-propyl acetate (PMA), make solid content and be 75% pet reaction thing, hydroxy radical content 11.1%;
Getting the pet reaction thing that the above-mentioned solid content of 80g is 75% joins in reaction vessel, be heated to after 100 DEG C, add 40g polysiloxane DC-217, the PMA that the tetrabutyl titanate of 0.3g is made catalyzer and 20g is solvent, continues to be warmed up to approximately 140 DEG C, dehydration, isothermal reaction 3～4 hours, cooling, then adds 15g bisphenol f type epoxy resin NPEF-170-a, add again propyl carbinol, dimethylbenzene equal solvent to stir 30 minutes, adjust resin viscosity 500～1500cps, solid part 60%.
Table 1 is the performance table of the prepared supercoat of embodiment 1-5 and comparative example 1-2, and its measurement mode is as follows:
(1) anti-yellowing property test
Resin is sprayed on to two surfaces through on the light aluminium sheet cleaning up, with after 280 DEG C of baking 10min, take out an aluminium sheet as on-gauge plate, an other aluminium sheet takes out as model in baking oven after 280 DEG C of baking 1hr, the xanthochromia situation of test sample plate top coat.Judgement criteria is as follows:
(2) acid resistance test
Resin is sprayed to phosphatization iron plate upper, with taking out as model after 280 DEG C of baking 10min; Water and acetic acid are mixed into 3% acetic acid mixing solutions with mass ratio, then acetum being put into pot boils with gas furnace, model is put into pot to be kept boiling to boil after 1 hour taking out, in 5 minutes, test adhesion property according to GB/T9286-1998, coating is without falling paint, nothing foaming, and grid adherence test is not fallen paint for qualified.
Table 1
As shown in Table 1, comparative example 1 is with the difference of embodiment 1, resin synthetic in comparative example 1 is not containing epoxy resin composition, comparative example 2 is with the difference of embodiment 4 with embodiment 2, comparative example 3, and in comparative example 2 and comparative example 3, the contained epoxy resin composition of resin is that resin adds after synthetic again.The resin-phase ratio of the resin of the embodiment of the present invention 1～5 and comparative example 1, has higher acid resistance; Compared with comparative example 2, the in the situation that of identical epoxy content, there is good capable of resisting high-temperature yellowing performance and acid resistance; Compared with comparative example 3, there is good capable of resisting high-temperature yellowing performance.
The foregoing is only preferred embodiment of the present invention, not in order to limit essence technology contents scope of the present invention, essence technology contents of the present invention is to be broadly defined in the claim scope of application, any technology entity or method that other people complete, if defined identical with the claim scope of application, also or a kind of change of equivalence, be all covered by among this claim scope being regarded as.
All documents of mentioning in the present invention are all quoted as a reference in this application, are just quoted separately as a reference as each section of document.In addition should be understood that, after having read foregoing of the present invention, those skilled in the art can make various changes or modifications the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (10)
1. a preparation method for organosilicon modified polyester epoxy resin, is characterized in that, comprises the following steps:
(a) provide the mixture of following component:
The pet reaction thing of hydroxy radical content 8～17.1%;
Polysiloxane;
The epoxy resin of hydroxyl and epoxide functional groups;
Optional polymerisation catalysts;
Wherein, the weight ratio of described polysiloxane and pet reaction thing is (30～90): (10～70);
The weight of the epoxy resin of described hydroxyl and epoxide functional groups account for described polysiloxane and pet reaction thing gross weight 5～15%;
Described polymerisation catalysts account for described polysiloxane and pet reaction thing gross weight 0～0.5%;
(b) described mixture reacts 3～4 hours under the temperature of reaction of 120～170 DEG C, obtains organosilicon modified polyester epoxy resin of the present invention.
2. the method for claim 1, is characterized in that, the polyester of described hydroxy radical content 8～17.1% obtains in accordance with the following steps:
Be that 1.65～3:1 adds polyvalent alcohol and polyprotonic acid by hydroxyl equivalent and carboxyl equivalent mol ratio, under the temperature of reaction of 180～230 DEG C, react to acid number for lower than 10mgKOH/g, obtain the pet reaction thing of hydroxy radical content 8～17.1%.
3. method as claimed in claim 2, is characterized in that,
Described polyvalent alcohol is TriMethylolPropane(TMP) and/or trimethylolethane; Or
Described polyprotonic acid is terephthalic acid and/or m-phthalic acid.
4. the method for claim 1, is characterized in that,
Described polysiloxane general formula is: R
1 a(R
2o)
bsiO
(4-a-b)/2,
Wherein,
R
1be selected from aromatic base, alkyl or thiazolinyl;
R
2be selected from H or alkyl; As described R
2while being selected from H, described R
2o is silicon hydroxyl, and the described polysiloxane silicon hydroxyl that contains 2～7wt%; As described R
2while being selected from alkyl, described R
2o is silicon alkoxyl group, and the described polysiloxane silicon alkoxyl group that contains 13～20wt%;
In formula, a+b=1～3, and b > 0, and be positive integer; Described polysiloxane contains at least one or the multiple repeating unit with following formula:
When a+b=1, contain T unit: R
1 a(R
2o)
bsiO
3/2;
When a+b=2, contain D unit: R
1 a(R
2o)
bsiO
2/2;
When a+b=3, contain M unit: R
1 a(R
2o)
bsiO
1/2;
Taking the total mole number of described polysiloxane as benchmark, described polysiloxane comprises T unit, the D unit of 0～15mol% and the M unit of 0～20mol% of 30～100mol%;
The weight-average molecular weight of described polysiloxane is 800～4000.
5. method as claimed in claim 4, is characterized in that, the silicon hydroxyl (R that described polysiloxane contains 2～6wt%
2for H) or the silicon alkoxyl group (R of 14～16wt%
2for alkyl).
6. method as claimed in claim 4, is characterized in that, described polysiloxane comprises T unit, the D unit of 0～10mol% and the M unit of 0～10mol% of 75～100mol%.
7. the method for claim 1, is characterized in that, described hydroxyl and the epoxy resin of epoxide functional groups are bisphenol A type epoxy resin, and epoxy equivalent (weight) is 450～1000.
8. the method for claim 1, it is characterized in that, described hydroxyl and the epoxy resin of epoxide functional groups by bisphenol f type epoxy resin and Bisphenol F or bisphenol S in molar ratio 2 ± 0.5:1 react and make for 3 ± 1 hours at 150 ± 30 DEG C, epoxy equivalent (weight) is 450～1000.
9. the method for claim 1, is characterized in that, described polymerisation catalysts is titanate ester catalyzer.
10. the organosilicon modified polyester epoxy resin that the method for claim 1 makes.
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| CN106047163A (en) * | 2016-06-28 | 2016-10-26 | 佛山市珀力玛高新材料有限公司 | Water-soluble organic silicon coating |
| CN106117559A (en) * | 2016-06-29 | 2016-11-16 | 佛山市珀力玛高新材料有限公司 | A kind of water-soluble organic silicon resin and preparation method thereof |
| WO2018001100A1 (en) * | 2016-06-28 | 2018-01-04 | 佛山市珀力玛高新材料有限公司 | Water-soluble organosilicon resin and application thereof |
| CN111253611A (en) * | 2020-03-19 | 2020-06-09 | 上海越科新材料股份有限公司 | PET foaming method |
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| CN106047163A (en) * | 2016-06-28 | 2016-10-26 | 佛山市珀力玛高新材料有限公司 | Water-soluble organic silicon coating |
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| CN106117559B (en) * | 2016-06-29 | 2019-06-07 | 佛山市珀力玛高新材料有限公司 | A kind of water-soluble organic silicon resin and preparation method thereof |
| CN111253611A (en) * | 2020-03-19 | 2020-06-09 | 上海越科新材料股份有限公司 | PET foaming method |
| CN111253611B (en) * | 2020-03-19 | 2022-07-05 | 上海越科新材料股份有限公司 | PET foaming method |
| CN112574420A (en) * | 2020-12-11 | 2021-03-30 | 广东四方威凯新材料有限公司 | Preparation method of silicon modified resin and silicon modified resin |
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