CN103897197B - The preparation method of organosilicon modified polyester epoxy resin - Google Patents
The preparation method of organosilicon modified polyester epoxy resin Download PDFInfo
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- CN103897197B CN103897197B CN201210585860.7A CN201210585860A CN103897197B CN 103897197 B CN103897197 B CN 103897197B CN 201210585860 A CN201210585860 A CN 201210585860A CN 103897197 B CN103897197 B CN 103897197B
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Abstract
The invention provides a kind of preparation method of organosilicon modified polyester epoxy resin, comprises the following steps：1) mixture of following component is provided：The pet reaction thing of hydroxy radical content 8～17.1%；Polysiloxanes；The epoxy resin of hydroxyl and epoxide functional groups；Optional polymerisation catalysts；Wherein, the polysiloxanes and the weight ratio of pet reaction thing are (30～90)：(10～70)；The weight of the epoxy resin of the hydroxyl and epoxide functional groups accounts for the 5～15% of the polysiloxanes and the gross weight of pet reaction thing；The polymerisation catalysts account for the 0～0.5% of the polysiloxanes and the gross weight of pet reaction thing；B () described mixture is reacted 3～4 hours under 120～170 DEG C of reaction temperature, obtain organosilicon modified polyester epoxy resin of the present invention.The present invention also provides the organosilicon modified polyester epoxy resin and its product.
Description
Technical field
The present invention relates to a kind of preparation method of resin, the especially 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 in terms of molecular structure, it has the two-fold advantage of organic siliconresin and polyester resin,
With excellent thermostability, tolerance to cold, weatherability, electric insulating quality and mechanical performance.Epoxy resin has good physics, changes
Performance is learned, its surface to metal and nonmetallic materials has excellent adhesive strength, and shrinkage factor is little, and good stability of the dimension is resistance to
Chemical property is excellent.If epoxy resin is combined with organosilicon polyester applying in coating, can improve coating adherence and
Decay resistance.
CN101307220A discloses a kind of organosilicon modified polyester electronic packaging material, contains asphalt mixtures modified by epoxy resin in its composition
The compositions such as fat, organosilicon modified polyester, using organosilicon modified polyester as the firming agent of epoxy resin, by premixing, melt
Mixing is made, with good resistance to water and electrical insulation capability.CN101885944A discloses a kind of organic silicon polyester resin and applies
Material, is dual-component coating, contains modified organic silicon polyester resin wherein in component A, and the modified organic silicon polyester resin is by organic
Silicon polyester resin is mixed to get with epoxy resin and other solvents；After by weight proportion mixing of the component A and component B by 1: 1
To organic silicon polyester resin coating.With toxicity it is low, construction application is convenient, film is tough and tensile, wear-resisting, cohesive force strong, permeability resistance
Good and etch resistant properties are excellent.
Technical scheme disclosed above is to adopt the method for mixing organosilicon polyester with epoxy resin product is obtained,
There is xanthochromia, it is impossible to suitable for the field of cook utensil when products obtained therefrom is used under the high temperature conditions.Therefore, ability
Domain a kind of overcomes the organosilicon polyester epoxy resin and preparation method that high temperature xanthochromia again can be acidproof in the urgent need to developing.
The content of the invention
The first object of the present invention is to obtain a kind of to overcome the organosilicon polyester asphalt mixtures modified by epoxy resin that high temperature xanthochromia again can be acidproof
Fat.
The second object of the present invention is to obtain a kind of to overcome the organosilicon polyester asphalt mixtures modified by epoxy resin that high temperature xanthochromia again can be acidproof
Fat preparation method.
A first aspect of the present invention provides a kind of preparation method of organosilicon modified polyester epoxy resin, and which includes following step
Suddenly：
A () provides the mixture of following component：
The pet reaction thing of hydroxy radical content 8～17.1%；
Polysiloxanes；
The epoxy resin of hydroxyl and epoxide functional groups；
Optional polymerisation catalysts；
Wherein, the polysiloxanes and the weight ratio of pet reaction thing are (30～90)：(10～70)；
It is total with pet reaction thing that the weight of the epoxy resin of the hydroxyl and epoxide functional groups accounts for the polysiloxanes
The 5～15% of weight；
The polymerisation catalysts account for the 0～0.5% of the polysiloxanes and the gross weight of pet reaction thing
B () described mixture is reacted 3～4 hours under 120～170 DEG C of reaction temperature, obtain of the present invention having
Machine silicon modified polyesterses epoxy resin.
In a specific embodiment of the present invention, the polyester of the hydroxy radical content 8～17.1% is obtained in accordance with the following steps
：
It is 1.65～3 according to hydroxyl equivalent is pressed with carboxyl equivalent mol ratio：1 adds polyhydric alcohol and polyprotic acid, 180～
It is pet reaction thing that hydroxy radical content 8～17.1% is obtained less than 10mgKOH/g to react under 230 DEG C of reaction temperature to acid number.
In a specific embodiment of the present invention, described polyhydric alcohol is trimethylolpropane and/or trihydroxy methyl
Ethane；Or
Described polyprotic acid is p-phthalic acid and/or M-phthalic acid.
In a specific embodiment of the present invention, described polysiloxanes formula is：R1 a(R2O)bSiO(4-a-b)/2,
Wherein,
R1Selected from aromatic radical, alkyl or thiazolinyl；
R2Selected from H or alkyl；As the R2Selected from H when, the R2O is silicone hydroxyl, and the polysiloxanes contain 2～
The silicone hydroxyl of 7wt%；As the R2Selected from alkyl when, the R2O is silane epoxide, and the polysiloxanes contain 13～20wt%
Silane epoxide；
In formula, a+b=1～3, and b ＞ 0, and it is positive integer；The polysiloxanes contain and at least one or more of have
The repetitives of following formula：
During a+b=1, containing T unit：R1 a(R2O)bSiO3/2；
During a+b=2, containing D units：R1 a(R2O)bSiO2/2；
During a+b=3, containing M units：R1 a(R2O)bSiO1/2；
On the basis of the total mole number of the polysiloxanes, the polysiloxanes include the T unit of 30～100mol%, 0～
The M units of the D units and 0～20mol% of 15mol%；
The weight average molecular weight of the polysiloxanes is 800～4000.
In a detailed embodiment, described polysiloxanes contain the silicone hydroxyl (R of 2～6wt%2For H) or 14～
Silane epoxide (the R of 16wt%2For alkyl).
In a detailed embodiment, described polysiloxanes include the T unit of 75～100mol%, 0～10mol%
The M units of D units and 0～10mol%.
In a detailed embodiment, described polysiloxanes contain the silicone hydroxyl (R of 2～6wt%2For H) or 14～
Silane epoxide (the R of 16wt%2For alkyl).
In a detailed embodiment, described polysiloxanes include the T unit of 75～100mol%, 0～10mol%
The M units of D units and 0～10mol%.
In a detailed embodiment, described polysiloxanes include the T unit and 5～15mol% of 85～95mol%
D units.
In a detailed embodiment, the R1The preferred phenyl of aromatic radical.
In a detailed embodiment, the R1Alkyl is selected from methyl, ethyl or propyl group.
In a detailed embodiment, the R1Thiazolinyl is selected from vinyl.
In a detailed embodiment, the R2Alkyl is selected from methyl, ethyl, propyl group or butyl.
In a detailed embodiment, described polysiloxanes are phenyl polysiloxane or methyl phenyl silicone.
In a detailed embodiment, described polysiloxanes contain the silicone hydroxyl (R of 2～6wt%2For H) or 14～
Silane epoxide (the R of 16wt%2For alkyl).
In a detailed embodiment, described polysiloxanes include the T unit of 75～100mol%, 0～10mol%
The M units of D units and 0～10mol%.
In a specific embodiment of the present invention, the epoxy resin of described hydroxyl and epoxide functional groups is bis-phenol
A type epoxy resin, epoxide equivalent are 450～1000.
In a specific embodiment of the present invention, the epoxy resin of described hydroxyl and epoxide functional groups is by bis-phenol
F types epoxy resin and Bisphenol F or bisphenol S in molar ratio 2 ± 0.5:1 is obtained in 150 ± 30 DEG C of reactions for 3 ± 1 hours, epoxide equivalent
For 450～1000.
In a specific embodiment of the present invention, described polymerisation catalysts are titanate ester catalyst.
A second aspect of the present invention provides organosilicon modified polyester asphalt mixtures modified by epoxy resin obtained in a kind of method as described in the present invention
Fat.
Specific embodiment
The present inventor by improving preparation method, obtains one kind and high temperature can be overcome yellow through extensively in-depth study
Become again can be acidproof organic silicon polyester resin and preparation method.The present invention is completed on this basis.
In the present invention, term " containing " or " including " represent that various composition can be applied to the mixture or group of the present invention together
In compound.Therefore, term " mainly by ... constitute " and " consist of " were included in term " containing " or " including ".
Hereinafter it is described 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 which includes following step
Suddenly：
A () provides the mixture of following component：
The pet reaction thing of hydroxy radical content 8～17.1%；
Polysiloxanes；
The epoxy resin of hydroxyl and epoxide functional groups；
Optional polymerisation catalysts；
Wherein, the polysiloxanes and the weight ratio of pet reaction thing are (30～90)：(10～70)；
It is total with pet reaction thing that the weight of the epoxy resin of the hydroxyl and epoxide functional groups accounts for the polysiloxanes
The 5～15% of weight；
The polymerisation catalysts account for the 0～0.5% of the polysiloxanes and the gross weight of pet reaction thing
B () described mixture is reacted 3～4 hours under 120～170 DEG C of reaction temperature, obtain of the present invention having
Machine silicon modified polyesterses epoxy resin.
The inventors discovered that, after being reacted using the component mixture, resulting organosilicon modified polyester asphalt mixtures modified by epoxy resin
Fat can overcome the high temperature xanthochromia again can be acidproof.
The order of addition of the step (a) is most preferably as follows：
By polysiloxanes and the pet reaction thing in mass ratio 30～90 of hydroxy radical content 8～17.1%：10～70 mixing, so
Epoxy resin, the Yi Jizhan of the hydroxyl and epoxide functional groups that account for polysiloxanes and pet reaction thing gross mass 5～15% are added afterwards
The polymerisation catalysts of all reactant gross mass 0～0.5%, react 3～4 hours under 120～170 DEG C of reaction temperature,
Obtain organosilicon modified polyester epoxy resin of the present invention.
In a specific embodiment of the present invention, the polyester of the hydroxy radical content 8～17.1% is obtained in accordance with the following steps
：
It is 1.65～3 according to hydroxyl equivalent is pressed with carboxyl equivalent mol ratio：1 adds polyhydric alcohol and polyprotic acid, 180～
It is pet reaction thing that hydroxy radical content 8～17.1% is obtained less than 10mgKOH/g to react under 230 DEG C of reaction temperature to acid number.
The acid number control of reaction system less than 10mgKOH/g, is obtained by inventor so as to control the polyreaction
" the pet reaction thing of hydroxy radical content 8～17.1% ".
The pet reaction thing of the hydroxy radical content 8～17.1% also can be obtained by other conventional polyester reactions, but instead
System is answered to need the acid number control of reaction system less than 10mgKOH/g.
The reaction system can also add appropriate solvent.The solvent should be atent solvent, not to the anti-of the present invention
Impact should be produced, such as appropriate propylene glycol methyl ether acetate (PMA).
In a specific embodiment of the present invention, described polyhydric alcohol is trimethylolpropane and/or trihydroxy methyl
Ethane；Or
Described polyprotic acid is p-phthalic acid and/or M-phthalic acid.
In a specific embodiment of the present invention, described polysiloxanes formula is：R1 a(R2O)bSiO(4-a-b)/2,
Wherein,
R1Selected from aromatic radical, alkyl or thiazolinyl；
R2Selected from H or alkyl；As the R2Selected from H when, the R2O is silicone hydroxyl, and the polysiloxanes contain 2～
The silicone hydroxyl of 7wt%；As the R2Selected from alkyl when, the R2O is silane epoxide, and the polysiloxanes contain 13～20wt%
Silane epoxide；
In formula, a+b=1～3, and b ＞ 0, and it is positive integer；The polysiloxanes contain and at least one or more of have
The repetitives of following formula：
During a+b=1, containing T unit：R1 a(R2O)bSiO3/2；
During a+b=2, containing D units：R1 a(R2O)bSiO2/2；
During a+b=3, containing M units：R1 a(R2O)bSiO1/2；
On the basis of the total mole number of the polysiloxanes, the polysiloxanes include the T unit of 30～100mol%, 0～
The M units of the D units and 0～20mol% of 15mol%；
The weight average molecular weight of the polysiloxanes is 800～4000.
In a detailed embodiment, described polysiloxanes contain the silicone hydroxyl (R of 2～6wt%2For H) or 14～
Silane epoxide (the R of 16wt%2For alkyl).
In a detailed embodiment, described polysiloxanes include the T unit of 75～100mol%, 0～10mol%
The M units of D units and 0～10mol%.
In a detailed embodiment, described polysiloxanes include the T unit and 5～15mol% of 85～95mol%
D units.
In a detailed embodiment, described polysiloxanes contain the silicone hydroxyl (R of 2～6wt%2For H) or 14～
Silane epoxide (the R of 16wt%2For alkyl).
In a detailed embodiment, described polysiloxanes include the T unit of 75～100mol%, 0～10mol%
The M units of D units and 0～10mol%.
In a detailed embodiment, the R1The preferred phenyl of aromatic radical.
In a detailed embodiment, the R1Alkyl is selected from methyl, ethyl or propyl group.
In a detailed embodiment, the R1Thiazolinyl is selected from vinyl.
In a detailed embodiment, the R2Alkyl is selected from methyl, ethyl, propyl group or butyl.
In a detailed embodiment, described polysiloxanes are phenyl polysiloxane or methyl phenyl silicone.
In a detailed embodiment, described polysiloxanes contain the silicone hydroxyl (R of 2～6wt%2For H) or 14～
Silane epoxide (the R of 16wt%2For alkyl).
In a detailed embodiment, described polysiloxanes include the T unit of 75～100mol%, 0～10mol%
The M units of D units and 0～10mol%.
In a specific embodiment of the present invention, the epoxy resin of described hydroxyl and epoxide functional groups is bis-phenol
A type epoxy resin, epoxide equivalent are 450～1000.
In a specific embodiment of the present invention, the epoxy resin of described hydroxyl and epoxide functional groups is by bis-phenol
F types epoxy resin and Bisphenol F or bisphenol S in molar ratio 2 ± 0.5:1 is obtained in 150 ± 30 DEG C of reactions for 3 ± 1 hours, epoxide equivalent
For 450～1000.
In a specific embodiment of the present invention, described polymerisation catalysts are titanate ester catalyst.
The titanate ester catalyst optionally can add.The phthalate catalyst for being adopted is not specifically limited,
As long as not producing restriction to the goal of the invention of the present invention.
It is specific to include but is not limited to：Phthalate catalyst is butyl titanate or isopropyl titanate.
Organosilicon modified polyester epoxy resin and its product
A second aspect of the present invention provides organosilicon modified polyester asphalt mixtures modified by epoxy resin obtained in a kind of method as described in the present invention
Fat.
The preferred embodiments of the present invention
It is an object of the invention to provide a kind of preparation method of organosilicon modified polyester epoxy resin, system of the present invention
Standby process is simple, side reaction are few, and yield is high；Gained organosilicon epoxy polyester have excellent heat-resisting, resisting high-temperature yellowing performance and
Acid resistance.
It is a further object of the present invention to provide a kind of organosilicon modified polyester epoxy resin, gained organosilicon epoxy polyester tool
There are excellent heat-resisting, 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) it is 1.65～3 to press hydroxyl equivalent with carboxyl equivalent mol ratio in reaction vessel：1 adds polyhydric alcohol and polynary
Acid, it is, less than 10mgKOH/g, to obtain the poly- of hydroxy radical content 8～17.1% to react under 180～230 DEG C of reaction temperature to acid number
Ester reactant；
2) by polysiloxanes and step 1) the pet reaction thing in mass ratio 30～90 that obtains：10～70 mixing, Ran Houjia
Enter to account for the epoxy resin of the hydroxyl and epoxide functional groups of polysiloxanes and pet reaction thing gross mass 5～15% and account for all
The polymerisation catalysts of reactant gross mass 0～0.5%, react 3～4 hours under 120～170 DEG C of reaction temperature, obtain
Organosilicon modified polyester epoxy resin of the present invention.
Described polyhydric alcohol is trimethylolpropane and/or trimethylolethane, can add on a small quantity ethyl butyl propanediol,
Neopentyl glycol, butanediol, Propylene Glycol.
Described polyprotic acid is p-phthalic acid and/or M-phthalic acid, can add on a small quantity trimellitic anhydride, succinic acid,
Adipic acid.
Described polysiloxanes formula is：R1 a(R2O)bSiO(4-a-b)/2, wherein, R1It preferably is selected from aromatic radical such as phenyl, alkyl
Such as methyl, ethyl or propyl group or thiazolinyl such as vinyl；R2It preferably is selected from H or alkyl such as methyl, ethyl, propyl group or butyl；It is described
Polysiloxanes contain the silicone hydroxyl (R of 2～7wt%2For H) or 13～20wt% silane epoxide (R2For alkyl), preferably comprise 2～
Silicone hydroxyl (the R of 6wt%2For H) or 14～16wt% silane epoxide (R2For alkyl).
In formula, a+b=1～3, and b ＞ 0；Polysiloxanes contain at least one or more of repetitives with following formula：
During a+b=1, T unit：R1 a(R2O)bSiO3/2；
During a+b=2, D units：R1 a(R2O)bSiO2/2；
During a+b=3, M units：R1 a(R2O)bSiO1/2。
On the basis of the total mole number of the polysiloxanes, the polysiloxanes include the T unit of 30～100mol%, 0～
The M units of the D units and 0～20mol% of 15mol%；Preferably include the T unit of 75～100mol%, the D units of 0～10mol% and
The M units of 0～10mol%.
The weight average molecular weight of the polysiloxanes is 800～4000.The polysiloxanes be more preferably phenyl polysiloxane,
Methyl phenyl silicone.
Described polymerisation catalysts are titanate ester catalyst, preferably butyl titanate or isopropyl titanate.
The epoxy resin of described hydroxyl and epoxide functional groups be bisphenol A type epoxy resin, epoxide equivalent be 450～
1000。
The epoxy resin of described hydroxyl and epoxide functional groups is massaged with Bisphenol F or bisphenol S by bisphenol f type epoxy resin
You compare 2:1 is obtained in 150 DEG C of reactions for 3 hours, and epoxide equivalent is 450～1000.
Preparation process is simple of the present invention, gained organosilicon modified polyester epoxy resin have significantly heat-resisting, resistance to Huang
Become performance, and preferably acid resistance.
As no specific instructions, various raw materials of the invention can be by being commercially available；Or according to the routine side of this area
Method is prepared.Unless otherwise defined or described herein, all specialties used herein are ripe with art technology with scientific words
Practice same meaning familiar to personnel institute.In addition any similar to described content or impartial method and material all can be applicable to this
In inventive method.
Above-mentioned synthetic method is the synthetic route of part of compounds of the present invention, according to above-mentioned example, people in the art
Member can synthesize other compounds of the present invention by adjusting different methods, or, those skilled in the art are according to existing
Known technology can synthesize the compound of the present invention.
Other aspects of the present invention, due to this disclosure, are apparent to those skilled in the art
's.
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limit the scope of the present invention.The experimental technique of unreceipted actual conditions in the following example, generally according to country's mark
It is accurate to determine.If no corresponding national standard, built according to general international standard, normal condition or according to manufacturer
The condition of view is carried out.Unless otherwise indicated, otherwise all of number is weight portion, and all of percentage ratio is weight percentage, institute
The polymer molecular weight stated is number-average molecular weight.
Unless otherwise defined or described herein, all specialties used herein and scientific words and the skilled people of art technology
Same meaning familiar to member institute.In addition any similar to described content or impartial method and material all can be applicable to the present invention
In method.
Nomenclature of drug and source used by the present invention is listed below, but is not limited only to listed medicine：
(1) polysiloxanes：
The DC-217 sold by Dow corning company, purified petroleum benzin based polysiloxane, R1It is phenyl and silicone hydroxyl (R2For H) contain
Measure as 6.0wt%；
The Silres IC678 sold by German Wa Ke companies, purified petroleum benzin based polysiloxane, R1It is phenyl and silicon methoxyl group (R2
For methyl) content be 14.0wt%；
The Silres REN168 sold by German Wa Ke companies, methyl phenyl silicone, phenyl and methyl (R1) mole
Than for 1.1:1.0, and silicone hydroxyl (R2For H) content be 4.0～5.0wt%.
(2) bisphenol A type epoxy resin：
The EPIKOTE sold by Momentive Specialty Chemicals Inc.TMResin1001, epoxide equivalent
450～500, solid；EPIKOTETMResin1004, epoxide equivalent 806～909, solid；
The NPES-904 sold by Nan Ya Plastics company, epoxide equivalent 780～850, solid.
(3) hydroxyl bisphenol f type epoxy resin：
NPEF-170-a：By 2mol (340g) bisphenol f type epoxy resin (NPEF- sold by Nan Ya Plastics company
170, epoxide equivalent 160～180, liquid) it is obtained within 3 hours in 150 DEG C of reactions with 1mol (200g) Bisphenol Fs, epoxide equivalent is
600。
NPEF-170-b：By 2mol (340g) bisphenol f type epoxy resin (NPEF- sold by Nan Ya Plastics company
170, epoxide equivalent 160～180, liquid) it is obtained within 3 hours in 150 DEG C of reactions with 1mol (250g) bisphenol Ss, epoxide equivalent is
650。
In order that one of ordinary skill in the art is more clearly understood that the feature of the present invention, following embodiments are now enumerated.
Embodiment 1
268g trimethylolpropanes, 166g M-phthalic acids are added in the reaction vessel for be connected with nitrogen, is heated to
Isothermal reaction after 220 DEG C, dehydration, when acid number drops to below 10mgKOH/g, is cooled to 140 DEG C, adds appropriate propylene glycol monomethyl ether
Acetate (PMA), prepared solid content is 75% pet reaction thing, hydroxy radical content 17.1%；
Take the pet reaction thing that the above-mentioned solid contents of 40g are 75% to be added in reaction vessel, after being heated to 100 DEG C, plus
Enter 70g polysiloxanes DC-217,8g bisphenol A type epoxy resin EPIKOTETMThe butyl titanate of Resin1001,0.5g is urged
The PMA of agent and 35g is solvent, continues to be warmed up to about 120 DEG C, is dehydrated, isothermal reaction 3～4 hours, and cooling is just subsequently adding
Butanol, dimethylbenzene equal solvent are stirred 30 minutes, adjustment 500～1500cps of resin viscosity, solid part 60%.
Embodiment 2
134g trimethylolpropanes, 60g trimethylolethanes, 166g are added in the reaction vessel for be connected with nitrogen to benzene two
Formic acid, isothermal reaction after being heated to 230 DEG C, dehydration, when acid number drops to below 10mgKOH/g, are cooled to 140 DEG C, plus
Enter appropriate propylene glycol methyl ether acetate (PMA), prepared solid content is 75% pet reaction thing, hydroxy radical content 13.1%；
Take the pet reaction thing that the above-mentioned solid contents of 60g are 75% to be added in reaction vessel, after being heated to 100 DEG C, plus
Enter 55g polysiloxanes Silres REN168,5g bisphenol A type epoxy resin EPIKOTETMThe metatitanic acid isopropyl of Resin1004,0.1g
It is solvent that ester makees catalyst and the PMA of 30g, continues to be warmed up to about 140 DEG C, is dehydrated, isothermal reaction 3～4 hours, cooling, then
N-butyl alcohol, dimethylbenzene equal solvent is added to stir 30 minutes, adjustment 500～1500cps of resin viscosity, solid part 60%.
Embodiment 3
134g trimethylolpropanes, 20.8g neopentyl glycols, 169.8g isophthalic two are added in the reaction vessel for be connected with nitrogen
Formic acid, isothermal reaction after being heated to 180 DEG C, dehydration, when acid number drops to below 10mgKOH/g, are cooled to 140 DEG C, plus
Enter appropriate propylene glycol methyl ether acetate (PMA), prepared solid content is 75% pet reaction thing, hydroxy radical content 8.0%；
Take the pet reaction thing that the above-mentioned solid contents of 100g are 75% to be added in reaction vessel, after being heated to 100 DEG C,
Add 25g polysiloxanes Silres IC678,10g bisphenol A type epoxy resin NPES-904, and the PMA of 20g to be solvent, continue
About 150 DEG C are warmed up to, separating methanol, isothermal reaction 3～4 hours, cooling are subsequently adding n-butyl alcohol, dimethylbenzene equal solvent stirring 30
Minute, adjustment 500～1500cps of resin viscosity, solid part 60%.
Embodiment 4
40.2g trimethylolpropanes, 120g trimethylolethanes, 83g are added in the reaction vessel for be connected with nitrogen to benzene
Dioctyl phthalate and 83g M-phthalic acids, isothermal reaction after being heated to 200 DEG C, dehydration, when acid number drops to below 10mgKOH/g
When, 140 DEG C are cooled to, appropriate propylene glycol methyl ether acetate (PMA) is added, prepared solid content is 75% pet reaction thing, hydroxyl
Content 11.1%；
Take the pet reaction thing that the above-mentioned solid contents of 80g are 75% to be added in reaction vessel, after being heated to 100 DEG C, plus
Enter 40g polysiloxanes DC-217, the butyl titanate of 15g bisphenol f type epoxy resin NPEF-170-a, 0.3g make catalyst and
The PMA of 28g be solvent, continue to be warmed up to about 140 DEG C, be dehydrated, isothermal reaction 3～4 hours, cooling, be subsequently adding n-butyl alcohol, two
Toluene equal solvent is stirred 30 minutes, adjustment 500～1500cps of resin viscosity, solid part 60%.
Embodiment 5
240g trimethylolethanes, 166g M-phthalic acids and the inclined benzene of 19.2g are added in the reaction vessel for be connected with nitrogen
Three anhydride, isothermal reaction after being heated to 220 DEG C, dehydration, when acid number drops to below 10mgKOH/g, are cooled to 140 DEG C,
Add appropriate propylene glycol methyl ether acetate (PMA), prepared solid content is 75% pet reaction thing, hydroxy radical content 16.4%；
Take the pet reaction thing that the above-mentioned solid contents of 120g are 75% to be added in reaction vessel, after being heated to 100 DEG C,
Add 10g polysiloxanes DC-217, the butyl titanate of 6g bisphenol f type epoxy resin NPEF-170-b, 0.1g make catalyst and
The PMA of 20g be solvent, continue to be warmed up to about 170 DEG C, be dehydrated, isothermal reaction 3～4 hours, cooling, be subsequently adding n-butyl alcohol, two
Toluene equal solvent is stirred 30 minutes, adjustment 500～1500cps of resin viscosity, solid part 60%.
Comparative example 1
268g trimethylolpropanes, 166g M-phthalic acids are added in the reaction vessel for be connected with nitrogen, is heated to
Isothermal reaction after 220 DEG C, dehydration, when acid number drops to below 10mgKOH/g, is cooled to 140 DEG C, adds appropriate propylene glycol monomethyl ether
Acetate (PMA), prepared solid content is 75% pet reaction thing, hydroxy radical content 17.1%；
Take the pet reaction thing that the above-mentioned solid contents of 40g are 75% to be added in reaction vessel, after being heated to 100 DEG C, plus
Enter 70g polysiloxanes DC-217, it is solvent that the butyl titanate of 0.5g makees catalyst and the PMA of 30g, continues to be warmed up to about 120
DEG C, dehydration, isothermal reaction 3～4 hours, cooling are subsequently adding n-butyl alcohol, dimethylbenzene equal solvent and stir 30 minutes, adjust resin
500～1500cps of viscosity, solid part 60%.
Comparative example 2
134g trimethylolpropanes, 60g trimethylolethanes, 166g are added in the reaction vessel for be connected with nitrogen to benzene two
Formic acid, isothermal reaction after being heated to 230 DEG C, dehydration, when acid number drops to below 10mgKOH/g, are cooled to 140 DEG C, plus
Enter appropriate propylene glycol methyl ether acetate (PMA), prepared solid content is 75% pet reaction thing, hydroxy radical content 13.1%；
Take the pet reaction thing that the above-mentioned solid contents of 60g are 75% to be added in reaction vessel, after being heated to 100 DEG C, plus
Enter 55g polysiloxanes Silres REN168, it is solvent that the isopropyl titanate of 0.1g makees catalyst and the PMA of 30g, continues to heat up
To about 140 DEG C, then dehydration, isothermal reaction 3～4 hours, cooling add 5g bisphenol A type epoxy resin EPIKOTETM
Resin1004, adds n-butyl alcohol, dimethylbenzene equal solvent and stirs 30 minutes, adjustment 500～1500cps of resin viscosity, solid part
60%。
Comparative example 3
40.2g trimethylolpropanes, 120g trimethylolethanes, 83g are added in the reaction vessel for be connected with nitrogen to benzene
Dioctyl phthalate and 83g M-phthalic acids, isothermal reaction after being heated to 200 DEG C, dehydration, when acid number drops to below 10mgKOH/g
When, 140 DEG C are cooled to, appropriate propylene glycol methyl ether acetate (PMA) is added, prepared solid content is 75% pet reaction thing, hydroxyl
Content 11.1%；
Take the pet reaction thing that the above-mentioned solid contents of 80g are 75% to be added in reaction vessel, after being heated to 100 DEG C, plus
Enter 40g polysiloxanes DC-217, it is solvent that the butyl titanate of 0.3g makees catalyst and the PMA of 20g, continues to be warmed up to about 140
DEG C, then dehydration, isothermal reaction 3～4 hours, cooling are added 15g bisphenol f type epoxy resin NPEF-170-a, add positive fourth
Alcohol, dimethylbenzene equal solvent are stirred 30 minutes, adjustment 500～1500cps of resin viscosity, solid part 60%.
The performance table of protective coating of the table 1 prepared by embodiment 1-5 and comparative example 1-2, it is as follows which measures mode：
(1) anti-yellowing property test
Resin spray through on the light aluminium sheet for cleaning up on two pieces of surfaces, after 280 DEG C of baking 10min, taking-up one
Block aluminium sheet is taken out exemplarily after toasting 1hr with 280 DEG C in an oven as on-gauge plate, in addition one block of aluminium sheet, test sample plate table
The xanthochromia situation of finishing coat.Evaluation criterion is as follows：
(2) acid resistance test
By on resin spray to phosphatization iron plate, take out exemplarily after toasting 10min with 280 DEG C；By water and acetic acid with matter
Amount ratio is mixed into 3% acetic acid mixed solution, then acetum is put in pot and boiled with gas stove, model is put in pot
Keep boiling boil 1 hour after take out, in 5 minutes according to GB/T9286-1998 test adhesion property, coating without fall paint, without foaming,
It is qualified that paint is not fallen in grid adherence test.
Table 1
As shown in Table 1, comparative example 1 is that the resin synthesized in comparative example 1 does not contain epoxy with the difference of embodiment 1
Resinous principle, comparative example 2 are to set in comparative example 2 and comparative example 3 with embodiment 2, comparative example 3 and the difference of embodiment 4
Epoxy resin ingredient contained by fat is to add after resins synthesis again.The resin of the embodiment of the present invention 1～5 and the resin of comparative example 1
Compare, with higher acid resistance；Compared with comparative example 2, in the case of identical epoxy content, with preferable high temperature resistant
Xanthochromia performance and acid resistance；Compared with comparative example 3, with preferable resisting high-temperature yellowing performance.
Presently preferred embodiments of the present invention is the foregoing is only, the substantial technological content model of the present invention is not limited to
Enclose, the substantial technological content of the present invention is broadly defined in the right of application, any technology that other people complete
Entity or method, if identical with defined in the right of application, also or a kind of equivalent change, will
Among being considered to be covered by the right.
The all documents referred in the present invention are all incorporated as reference in this application, independent just as each document
It is incorporated as with reference to such.In addition, it is to be understood that after the above for having read the present invention, those skilled in the art can be right
The present invention makes various changes or modifications, and these equivalent form of values equally fall within the application appended claims limited range.
Claims (10)
1. a kind of preparation method of organosilicon modified polyester epoxy resin, it is characterised in that comprise the following steps：
A () provides the mixture of following component：
The pet reaction thing of hydroxy radical content 8～17.1%；
Polysiloxanes；
The epoxy resin of hydroxyl and epoxide functional groups；
Optional polymerisation catalysts；
Wherein, the polysiloxanes and the weight ratio of pet reaction thing are (30～90)：(10～70)；
The weight of the epoxy resin of the hydroxyl and epoxide functional groups accounts for the gross weight of the polysiloxanes and pet reaction thing
5～15%；
The polymerisation catalysts account for the 0～0.5% of the polysiloxanes and the gross weight of pet reaction thing；
B () described mixture is reacted 3～4 hours under 120～170 DEG C of reaction temperature, obtain described organic-silicon-modified poly-
Ester epoxy resin.
2. the method for claim 1, it is characterised in that the polyester of the hydroxy radical content 8～17.1% is according to following step
It is rapid to obtain：
It is 1.65～3 by hydroxyl equivalent and carboxyl equivalent mol ratio：1 adds polyhydric alcohol and polyprotic acid, anti-at 180～230 DEG C
Should at a temperature of to react to acid number be pet reaction thing that hydroxy radical content 8～17.1% is obtained less than 10mgKOH/g.
3. method as claimed in claim 2, it is characterised in that
Described polyhydric alcohol is trimethylolpropane and/or trimethylolethane；Or
Described polyprotic acid is p-phthalic acid and/or M-phthalic acid.
4. the method for claim 1, it is characterised in that
Described polysiloxanes formula is：R1 a(R2O)bSiO(4-a-b)/2,
Wherein,
R1Selected from aromatic radical, alkyl or thiazolinyl；
R2Selected from H or alkyl；As the R2Selected from H when, the R2O is silicone hydroxyl, and the polysiloxanes contain 2～7wt%
Silicone hydroxyl；As the R2Selected from alkyl when, the R2O is silane epoxide, and the polysiloxanes contain the silicon of 13～20wt%
Alkoxyl；
In formula, a+b=1～3, and b ＞ 0, and it is positive integer；The polysiloxanes contain at least one or more of with following formula
Repetitives：
During a+b=1, containing T unit：R1 a(R2O)bSiO3/2；
During a+b=2, containing D units：R1 a(R2O)bSiO2/2；
During a+b=3, containing M units：R1 a(R2O)bSiO1/2；
On the basis of the total mole number of the polysiloxanes, the polysiloxanes include the T unit of 30～100mol%, 0～
The M units of the D units and 0～20mol% of 15mol%；
The weight average molecular weight of the polysiloxanes is 800～4000.
5. method as claimed in claim 4, it is characterised in that described polysiloxanes contain 2～6wt%R2For the silicone hydroxyl of H
Or 14～16wt%R2For the silane epoxide of alkyl.
6. method as claimed in claim 4, it is characterised in that described polysiloxanes include 75～100mol% T unit,
The M units of the D units and 0～10mol% of 0～10mol%.
7. the method for claim 1, it is characterised in that the epoxy resin of described hydroxyl and epoxide functional groups is double
Phenol A type epoxy resin, epoxide equivalent are 450～1000.
8. the method for claim 1, it is characterised in that the epoxy resin of described hydroxyl and epoxide functional groups is by double
Phenol F types epoxy resin and Bisphenol F or bisphenol S in molar ratio 2 ± 0.5:1 is obtained in 150 ± 30 DEG C of reactions for 3 ± 1 hours, and epoxy is worked as
Measure as 450～1000.
9. the method for claim 1, it is characterised in that described polymerisation catalysts are titanate ester catalyst.
10. organosilicon modified polyester epoxy resin obtained in a kind of the method for claim 1.
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| CN106047163B (en) * | 2016-06-28 | 2018-05-18 | 佛山市珀力玛高新材料有限公司 | A kind of water-soluble organic silicon coating |
| 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 |
| 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 |
| CN105968325B (en) * | 2016-06-29 | 2018-10-02 | 佛山市珀力玛高新材料有限公司 | A kind of organosilicon modified polyester epoxy resin with resisting high-temperature yellowing performance |
| 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 |
| CN115926468B (en) * | 2023-01-03 | 2023-11-07 | 湖北隆胜四海新材料股份有限公司 | Interpenetrating network type organic silicon resin and preparation method thereof |
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| JPS6072957A (en) * | 1983-09-30 | 1985-04-25 | Mitsui Toatsu Chem Inc | Curable composition |
| CN1902262A (en) * | 2003-12-23 | 2007-01-24 | 瓦克化学股份公司 | Solid siliconized polyester resin for powder coating |
| CN101307220A (en) * | 2008-07-10 | 2008-11-19 | 天津市凯华绝缘材料有限公司 | Organosilicon modified polyester electronic packaging material |
| CN102532556A (en) * | 2011-11-17 | 2012-07-04 | 杭州师范大学 | Chemical method for preparing organic silicon modified epoxy resin |
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| JPS6072957A (en) * | 1983-09-30 | 1985-04-25 | Mitsui Toatsu Chem Inc | Curable composition |
| CN1902262A (en) * | 2003-12-23 | 2007-01-24 | 瓦克化学股份公司 | Solid siliconized polyester resin for powder coating |
| CN101307220A (en) * | 2008-07-10 | 2008-11-19 | 天津市凯华绝缘材料有限公司 | Organosilicon modified polyester electronic packaging material |
| CN102532556A (en) * | 2011-11-17 | 2012-07-04 | 杭州师范大学 | Chemical method for preparing organic silicon modified epoxy resin |
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