CN108314796B - High temperature resistance polyester composite material and preparation method - Google Patents
High temperature resistance polyester composite material and preparation method Download PDFInfo
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- CN108314796B CN108314796B CN201810206393.XA CN201810206393A CN108314796B CN 108314796 B CN108314796 B CN 108314796B CN 201810206393 A CN201810206393 A CN 201810206393A CN 108314796 B CN108314796 B CN 108314796B
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/10—Block- or graft-copolymers containing polysiloxane sequences
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Abstract
The invention discloses a kind of high temperature resistance polyester composite material and preparation methods；With fluorine-containing phenyl polysiloxane and silicon rubber (107 glue) for raw material, SILICONE COATING AGENT is made by polycondensation reaction, the mixture of SILICONE COATING AGENT, oxidant, diluent is coated on polyester base material, drying, solidification obtain high temperature resistance polyester composite material.The advantages of a certain amount of containing fluorophenyl due to introducing in product structure, obtained product high temperature resistance and adhesive property is excellent, and has preparation process simple, low for equipment requirements, is suitble to industrial amplification production.
Description
Technical field
The present invention relates to a kind of high temperature resistance polyester composite material and preparation methods, belong to heat-resisting material preparation field.
Background technique
Polyester material is widely used, wherein the polyester material containing adhesive layer includes polyester base material and adhesive layer, high temperature resistant
Field generally uses organosilicon material as adhesive layer.The effective component of SILICONE COATING AGENT stick is organic siliconresin and organic
The product of polycondensation reaction occurs for silicon rubber (also known as 107 glue), by the way that organic solvent diluting is added into certain solid content, and adds friendship
Connection agent and other additives obtain product.Wherein, the main function of organic silicon rubber is to confer to coating agent with necessary cohesive force,
107 glue for being usually used in synthesizing organo-silicon coating agent are horizontal with 100,000 ~ 500,000 number-average molecular weight, are generally nothing at room temperature
The transparent very viscous thick liquid of color or semisolid；Silanol groups containing polarized in organic siliconresin molecular structure are provided to coating agent
Wetting ability, tack and peeling force.
The most widely used silicone resin in prepares coating agent is methyl silicon resin (referred to as MQ resin), with raw material valence
Honest and clean, the advantages that processing performance is good.But it is not good enough by the SILICONE COATING AGENT heat resistance that methyl silicon resin synthesizes, this
Type coating agent may fail when used for a long time under the hot conditions more than 300 DEG C, this is because methyl in adhesive macromolecular
The thermal decomposition of the organic groups such as silicon substrate, increases the adhesive degree of cross linking sharply.Methyl silicon resin is substituted using phenyl polysiloxane, it is heat-resisting
Performance is slightly good, but higher than will appear unsticking, embrittlement after being used for a long time under 300 DEG C of ultra-high temperature condition phenomena such as.
Summary of the invention
The present invention provides a kind of fluorine-containing resistance to for the insufficient status of high temperature resistance existing for existing SILICONE COATING AGENT
The method that high temperature silicone coating agent and high-temperaure coating agent prepare high temperature resistance polyester composite material, disclosed organosilicon apply
Layer agent stick has the high temperature resistant even characteristic of superhigh temperature resistant.
To reach goal of the invention of the present invention, the technical solution adopted is as follows:
A kind of high temperature resistance polyester composite material, the high temperature resistance polyester composite material include polyester base material and are coated on poly-
SILICONE COATING AGENT on ester group material；
The chemical structural formula of the SILICONE COATING AGENT is as follows:
Wherein, m=5~20；N=1~5；P=1~8；X=0~6；Y=1~10.
The preparation method of above-mentioned high temperature resistance polyester composite material includes the following steps:
(1) activator solution is added dropwise in the mixture of 107 sol solutions and catalyst, the tree of silicon containing fluorophenyl is then added
Lipoprotein solution, reflux water-dividing reaction, obtains polycondensation product；
(2) after mixing polycondensation product with curing agent, organic solvent, heat preservation curing obtains SILICONE COATING AGENT；
(3) by the mixture coating of SILICONE COATING AGENT, oxidant, diluent on polyester base material, drying, solidification are obtained
High temperature resistance polyester composite material；
The chemical structural formula of the fluorine-containing phenyl polysiloxane are as follows:
。
In the present invention, the activator, 107 peptizations, catalyst, fluorine-containing phenyl polysiloxane mass ratio be (0.005~
0.05): 1: (0.005~0.06): (1~10)；The mass ratio of the polycondensation product and curing agent is (0.02~0.5): (0.02
~0.3)；The SILICONE COATING AGENT, oxidant, solvent mass ratio be (1~3): 100: (0.04~0.06).
In the present invention, solvent is aromatic hydrocarbon solvent in the activator solution；Solvent is arene in 107 sol solutions
Solvent；Solvent is aromatic hydrocarbon solvent in the fluorine-containing phenyl polysiloxane solution；The organic solvent is isopropanol；The curing
Agent is hexamethyldisilazane；The catalyst is dibutyl tin dilaurate；The activator is dimethylformamide dimethyl oxygroup silicon
Alkane or dimethyl diethoxysilane；The oxidant is dibenzoyl peroxide or peroxidating -2,4 dichloro benzene formyl.
In the present invention, in step (1), at 80 DEG C ~ 100 DEG C, catalyst is added in 107 sol solutions；Then nitrogen is protected
Under shield, activator solution is added dropwise, is added dropwise to complete rear insulation reaction 1 ~ 6 hour；Then fluorine-containing phenyl polysiloxane solution is added, in
100 ~ 140 DEG C of reflux water-dividings react 2 ~ 60h, obtain polycondensation product；
In step (2), the temperature for keeping the temperature curing is 100 ~ 140 DEG C, and the time is 1 ~ 6 hour；
In step (3), drying is to dry 2min at 90 DEG C, is cured as solidifying 5 min at 150 DEG C.
In the present invention, the time that activator solution is added dropwise is 0.5 ~ 3 hour.
In the present invention, the preparation method of the fluorine-containing phenyl polysiloxane the following steps are included:
(1) pentafluorostyrene is dissolved in aromatic hydrocarbon solvent, precious metal salt catalyst is added under nitrogen protection；Then
Dimethyl dichlorosilane (DMCS) is added dropwise at 50~140 DEG C；It is added dropwise to complete rear insulation reaction 1 ~ 10 hour, prepares phenyl-pentafluoride ethyl dimethyl
Chlorosilane；
(2) in organic solvent by water, inorganic acid dispersion, phenyl-pentafluoride ethyl dimethyl chloride is then added dropwise at 60~80 DEG C
The mixture of silane and ethyl orthosilicate, heat preservation carries out a polycondensation 0.5~1 hour after being added dropwise to complete；Then three hydrocarbon are added dropwise again
The mixture of base one chlorosilane and ethyl orthosilicate, heat preservation carries out polycondensation reaction 1~6 hour again after being added dropwise to complete, and preparation contains
Fluorophenyl silicone resin.
In the present invention, pentafluorostyrene, precious metal salt, dimethyl dichlorosilane (DMCS) mass ratio be 1: (0.003~0.006):
(0.5~2)；In the mixture of phenyl-pentafluoride ethyl dimethylchlorosilane and ethyl orthosilicate, phenyl-pentafluoride ethyl dimethylchlorosilane
Mass ratio with ethyl orthosilicate is (1~6): (1~10)；In the mixture of one chlorosilane of trialkyl and ethyl orthosilicate, three
The mass ratio of one chlorosilane of alkyl and ethyl orthosilicate is (1~3): (1~10)；The precious metal salt is chloroplatinic acid；Described three
One chlorosilane of alkyl is trim,ethylchlorosilane, one chlorosilane of dimethyl hydrogen-based, one chlorosilane of dimethyl ethenyl, pheiiyldimetliyl
One of one chlorosilane；The inorganic acid is the concentrated sulfuric acid or concentrated hydrochloric acid.
In the present invention, the time that dimethyl dichlorosilane (DMCS) is added dropwise is 0.5~5 hour；One chlorosilane of trialkyl and positive silicon is added dropwise
The time of the mixture of acetoacetic ester is 0.5 ~ 1 hour；After reaction, reaction solution obtains step (1) by being evaporated off, being evaporated under reduced pressure
Phenyl-pentafluoride ethyl dimethylchlorosilane；Step (2) is again after polycondensation reaction, and reaction solution is through supercooling, vacuum distillation, liquid separation
Processing, extraction, distillation water washing, drying, filtering, distillation obtain fluorine-containing phenyl polysiloxane.
The invention also discloses fluorine-containing phenyl polysiloxanes or SILICONE COATING AGENT to prepare high temperature resistance polyester composite material
In application；The chemical structural formula of the fluorine-containing phenyl polysiloxane are as follows:
The chemical structural formula of the SILICONE COATING AGENT is as follows:
Wherein, m=5~20；N=1~5；P=1~8；X=0~6；Y=1~10.
Aromatic hydrocarbon solvent of the invention is that any one in toluene and dimethylbenzene or both is mixed according to arbitrary proportion
Mixed solvent；It is preferred that the reflux water-dividing time is 2 ~ 60 hours, preferably 12 ~ 24 hours.
Fluorine-containing phenyl polysiloxane and 107 glue disclosed by the invention pass through the reaction equation of polycondensation reaction synthesizing organo-silicon coating agent
It is as follows:
Wherein, m=5~20；N=1~5；P=1~8；X=0~6；Y=1~10；
R= -CH3Or-CH2CH3。
High temperature resistance polyester composite material preparation process includes polycondensation reaction and post-processing, gluing three-step reaction, can specifically be lifted
Under such as:
(1) polycondensation reaction
By weight, 1 part of 107 glue is dissolved in 0.5~10 part of aromatic hydrocarbon solvent, stirring is warming up to 80 DEG C ~ 100
DEG C, add 0.005 ~ 0.06 part of dibutyl tin dilaurate (DBTL).Under nitrogen protection, 0.005 ~ 0.05 part of activator dissolution is added dropwise
Solution in 0.1 ~ 0.5 part of aromatic hydrocarbon solvent adds for 0.5 ~ 3 hour, adds rear insulation reaction 1 ~ 6 hour.Then, it is added
1~10 part of fluorine-containing phenyl polysiloxane is dissolved in the solution in 1~10 part of aromatic hydrocarbon solvent, increases temperature to 100 ~ 140 DEG C, returns
Flow point water reacts 2 ~ 60h；
(2) it cures
By weight, 0.02 ~ 0.5 part of curing agent hexamethyldisilazane and 0.02 ~ 0.3 part are added in above-mentioned polycondensation product
Isopropanol, insulation reaction 1 ~ 6 hour.Stop reaction after curing, reaction solution is cooled to room temperature, discharging obtains organosilicon painting
Layer agent；
(3) gluing
Toluene 200g, SILICONE COATING AGENT 4g and dibenzoyl peroxide (BPO) 0.1g are sequentially added in a reservoir, are stirred
After uniformly, for obtained dilution glue with glue spreader gluing on polyester film, control bondline thickness is 0.05 ~ 0.06mm.Gluing
2min is dried at 90 DEG C afterwards, then 5 min of drying solidifies at 150 DEG C.
The preparation method of fluorine-containing phenyl polysiloxane of the invention, specifically can be as follows:
(1) hydrosilylation
By weight, 1 part of pentafluorostyrene is dissolved in 1~10 part of aromatic hydrocarbon solvent, chlorine is added under nitrogen protection
0.003 ~ 0.006 part of platinic acid catalyst, after being heated to 50 ~ 140 DEG C, in certain time be added dropwise 0.5 ~ 2 part of dimethyl dichlorosilane (DMCS),
Drip subsequent continuous insulation reaction 1 ~ 10 hour.After reaction, solvent and unreacted dimethyl dichlorosilane (DMCS) is evaporated off, decompression is steamed
It evaporates and collects 132 DEG C of fractions (3.75kPa), obtain phenyl-pentafluoride ethyl dimethylchlorosilane；
(2) polycondensation synthesizes silicone resin
Mixed silanes: by weight, by 1 ~ 3 part of one chlorosilane monomer, 1 ~ 6 part of phenyl-pentafluoride ethyl dimethylchlorosilane and 2 ~
20 parts of ethyl orthosilicate mixing, obtain mixed silanes；
Polycondensation reaction: by weight, 1 ~ 5 part of water and 0.5 ~ 2 part of inorganic acid being dispersed in 1 ~ 20 part of tetrahydrofuran, heating
After so that mixture temperature is risen to 60 ~ 80 DEG C, above-mentioned mixed silanes are added dropwise at a slow speed, drip within about 0.5 ~ 2 hour.Add subsequent continuation of insurance
Temperature reaction 1 ~ 6 hour；
Post-processing: after reaction solution cooling, vacuum distillation removes coproduct ethanol and solvents tetrahydrofurane, the temperature of distillation
It is 40~80 DEG C, vacuum degree is 0.5~20mmHg.Reaction solution remaining after distillation is poured into separatory funnel, with extractant extraction 3
~ 5 times, 1 ~ 5 part of extractant is used every time.Combining extraction liquid uses 1 ~ 5 part of distilled water to distill water washing 3 ~ 5 times every time.Again
It is added 0.2 ~ 1 part desiccant dryness 0.5 ~ 5 hour.It is filtered to remove desiccant, the bulk solids product that distillation obtains white is fluorine-containing
Phenyl polysiloxane, the temperature of distillation are 40~80 DEG C, and vacuum degree is 0.5~20mmHg.
The outstanding advantages of the present invention compared with prior art are:
1, methyl silicon resin, vinyl polysiloxane and phenyl polysiloxane are used not with traditional SILICONE COATING AGENT preparation
Together, the present invention prepares SILICONE COATING AGENT by raw material of pentafluorophenyl group modified silicone resin, and product has very superior heat resistance
Energy.
2, high-temperature resistant silicone coating agent provided by the invention joined activator activation in adhesive preparation process,
This can overcome the extremely strong pentafluorophenyl group of rigidity to introduce the reactive compromises after silicone resin；But activator can make adhesive resistance to
Hot property is deteriorated, therefore hexamethyldisilazane, which is added, before reaction terminates cures adhesive；Thus the polyester prepared is compound
Material peel strength is 40.5N(2.5cm), compression resistant and oxidation reach 72h at 325 DEG C, remain to after exposure from metal at 260 DEG C
Surface successfully removes.
3, fluorine-containing phenyl polysiloxane and 107 glue ratios can easily be accommodated in high-temperature resistant silicone coating agent provided by the invention,
Preparation is facilitated to adapt to the adhesive of different heat resistant requirements；And raw material used in preparation method of the present invention are easy to get, synthesis
Simple process is suitble to industrialized production.
Detailed description of the invention
Fig. 1 is coating agent thermogravimetric curve figure of the present invention.
Specific embodiment
Technical solution of the present invention is further elaborated with reference to the accompanying drawings and examples.
The present invention contains fluorophenyl using pentafluorophenyl group silicone resin and 107 glue of high molecular weight as raw material, by polycondensation reaction synthesis
SILICONE COATING AGENT, product introduce pentafluorophenyl group modified silicone resin, since pentafluorophenyl group has the planar structure and difficulty of conjugation
To be pyrolyzed the carbon-fluorine bond of scission of link, product has very superior heat resistance.
Embodiment one
(1) fluorine-containing phenyl polysiloxane is synthesized
5L three-necked flask is equipped with thermometer, reflux condensing tube and constant pressure dropping funnel, oil bath heating.Sequentially add 800g
Chloroplatinic acid catalyst 2.6g is added under nitrogen protection for toluene and 650g pentafluorostyrene, stirring and dissolving.Heating is opened, is warming up to
After 80 DEG C, 510g dichloromethylsilane is added dropwise, 30min is added, and time for adding is controlled at 1 hour or so.Continue after dripping
Insulation reaction 2 hours.After reaction, solvent and unreacted dimethyl dichlorosilane (DMCS) is evaporated off, 132 DEG C of fractions are collected in vacuum distillation
(3.75kPa) obtains phenyl-pentafluoride ethyl dimethylchlorosilane 950g, and it is 96.6% that gas-chromatography, which measures product purity, yield 90.9%.
In 250mL conical flask just by 80g tri-methyl-chlorosilane, 194g phenyl-pentafluoride ethyl dimethylchlorosilane and 630g
Silester is uniformly mixed, and obtains mixed silanes, spare.
500mL three-necked flask is equipped with thermometer, reflux condensing tube and constant pressure dropping funnel, oil bath heating.First by 80g water
It carefully slowly keys in 500g tetrahydrofuran with the 50g concentrated sulfuric acid, after heating makes mixture temperature rise to 70 DEG C, is added dropwise at a slow speed above-mentioned
The mixed silanes prepared in advance, time for adding are controlled in 45min or so.Add subsequent continuous insulation reaction 6 hours.Stop reaction,
Reaction solution, which is first evaporated under reduced pressure, removes coproduct ethanol and solvents tetrahydrofurane, and the temperature of distillation is 60 DEG C, vacuum degree 10mmHg,
Distillation is until no liquid distillates.Toluene extracts 3 times, the use of toluene amount is every time 300g.Combining extraction liquid, to distill water washing
5 times, 150g distilled water is used every time.After washing, it is 5 hours dry to add 60g anhydrous sodium sulfate.It is filtered to remove drying
Agent, distillation obtains the fluorine-containing phenyl polysiloxane of bulk solids product of white under the conditions of temperature is 80 DEG C, vacuum degree is 0.5mmHg
380g。
(2) polycondensation reaction
2L three-necked flask is equipped with thermometer, water segregator and reflux condensing tube, constant pressure addition funnel, oil bath heating.Successively plus
Enter 107 glue of 180g and 160g toluene, stirring is warming up to 80 DEG C, adds 1.7g dibutyl tin dilaurate (DBTL).Logical nitrogen, drop
1.2g dimethyl diethoxysilane is added to be dissolved in the solution in 20g toluene, 30min is added, insulation reaction 3h.Then, it is added
The fluorine-containing phenyl polysiloxane of 220g is dissolved in the solution in 210g toluene, increases temperature to 110 DEG C, reflux water-dividing reacts for 24 hours.
(3) it post-processes
Hexamethyldisilazane 12g, isopropanol 4.6g is added in polycondensation product, keeps the temperature slaking reaction 5h.Stop after reaction
It only reacts, cooling, discharging obtains high-temperaure coating agent.In maturing process, the silicone hydroxyl not being condensed on a small quantity further reacts.
(4) coating technique
Toluene 200g, the above-mentioned 4g of SILICONE COATING AGENT containing fluorophenyl and dibenzoyl peroxide are sequentially added in a reservoir
(BPO) 0.1g, after mixing evenly, obtained dilution glue is on polyester film (500 microns of thickness) with glue spreader gluing, control
Coating layer thickness is 0.05 ~ 0.06mm.2min is dried after gluing at 90 DEG C, then 5 min of drying solidifies at 150 DEG C, obtains resistance to
Hot polyester composite.
(5) performance test
Measuring heat-resistant polyester composite material peel strength according to GB/T 2792-1998 is 40.5N(2.5cm).According to GB/T
17875-1999 measures the organic silicon coating of heat-resistant polyester composite material, and compression resistant and oxidation are up to 72h at 325 DEG C, at 260 DEG C
It remains to successfully remove from metal surface after exposure.
The molecular structure of above-mentioned SILICONE COATING AGENT product is as follows:
Wherein, m=8~10；n =1~3；p=1~3；X=1~5；Y=2~6.
Embodiment two
(1) fluorine-containing phenyl polysiloxane step is synthesized with embodiment one.
(2) polycondensation reaction
2L three-necked flask is equipped with thermometer, water segregator and reflux condensing tube, constant pressure addition funnel, oil bath heating.Successively plus
Enter 170g107 glue and 165g dimethylbenzene, stirring is warming up to 90 DEG C, adds 1.5g dibutyl tin dilaurate (DBTL).Logical nitrogen, drop
1g dimethyldimethoxysil,ne is added to be dissolved in the solution in 20g dimethylbenzene, 30min is added, insulation reaction 3h.Then, it is added
The fluorine-containing phenyl polysiloxane of 325g is dissolved in the solution in 200g dimethylbenzene, increases temperature to 138 DEG C, reflux water-dividing reacts for 24 hours.
(3) it post-processes
Hexamethyldisilazane 15g, isopropanol 6.5g, insulation reaction 5h is added in polycondensation product.Stop after reaction anti-
It answers, cooling, discharging obtains high-temperaure coating agent.
(4) coating technique
Dimethylbenzene 200g, the 4g of SILICONE COATING AGENT containing fluorophenyl and peroxidating -2,4- dichloro-benzenes are sequentially added in a reservoir
Formyl 0.1g, after mixing evenly, obtained dilution glue is on polyester film (500 microns of thickness) with glue spreader gluing, control
Bondline thickness is 0.05 ~ 0.06mm.2min is dried after gluing at 100 DEG C, then at 130 DEG C 5 min of drying solidify to obtain it is resistance to
Hot polyester composite.
(5) bonding test
Measuring heat-resistant polyester composite material peel strength according to GB/T 2792-1998 is 31.5N(2.5cm).According to GB/T
17875-1999 measures the SILICONE COATING AGENT of heat-resistant polyester composite material, and compression resistant and oxidation are up to 72h at 325 DEG C, and 260 DEG C
It remains to successfully remove from metal surface after lower exposure.
The molecular structure of above-mentioned SILICONE COATING AGENT is as follows:
Wherein, m=6~12；n =1~3；p=1~3；X=2~5；Y=3~8.
Embodiment three
(1) polycondensation reaction
2L three-necked flask is equipped with thermometer, water segregator and reflux condensing tube, constant pressure addition funnel, oil bath heating.Successively plus
Enter 169g107 glue and 180g dimethylbenzene, stirring is warming up to 80 DEG C, adds 1.5g dibutyl tin dilaurate (DBTL).Logical nitrogen, drop
1g dimethyldimethoxysil,ne is added to be dissolved in the solution in 20g dimethylbenzene, 30min is added, insulation reaction 3h.Then, it is added
The fluorine-containing phenyl polysiloxane of 320g is dissolved in the solution in 200g dimethylbenzene, increases temperature to 140 DEG C, reflux water-dividing reacts 48h.
(2) it post-processes
Hexamethyldisilazane 15g, isopropanol 6.5g, insulation reaction 5h is added in polycondensation product.Stop after reaction anti-
It answers, cooling, discharging obtains high-temperaure coating agent.
(3) coating technique
Toluene 200g, the 4g of SILICONE COATING AGENT containing fluorophenyl and diphenyl peroxide base formyl are sequentially added in a reservoir
(BPO) 0.1g, after mixing evenly, obtained dilution glue is on polyester film (600 microns of thickness) with glue spreader gluing, control
Bondline thickness is 0.05 ~ 0.06mm.2min is dried after gluing at 100 DEG C, then at 150 DEG C 5 min of drying solidify to obtain it is resistance to
Hot polyester composite.
(4) bonding test
Measuring heat-resistant polyester composite material peel strength according to GB/T 2792-1998 is 30.3N(2.5cm).According to GB/T
17875-1999 measures the SILICONE COATING AGENT of heat-resistant polyester composite material, and compression resistant and oxidation are up to 72h at 325 DEG C, and 260 DEG C
It remains to successfully remove from metal surface after lower exposure.The molecular structure of above-mentioned SILICONE COATING AGENT is as follows:
Wherein, m=5~12；n =2~4；p=2~4；X=2~5；Y=3~7.
Example IV
(1) polycondensation reaction
2L three-necked flask is equipped with thermometer, water segregator and reflux condensing tube, constant pressure addition funnel, oil bath heating.Successively plus
Enter 140g107 glue and 150g toluene, stirring is warming up to 80 DEG C, adds 1.5g dibutyl tin dilaurate (DBTL).Logical nitrogen, is added dropwise
1g dimethyl diethoxysilane is dissolved in the solution in 18g toluene, and 30min is added, insulation reaction 3h.Then, 325g is added
Fluorine-containing phenyl polysiloxane is dissolved in the solution in 200g toluene, increases temperature to 110 DEG C, reflux water-dividing reacts 20h.
(2) it post-processes
Hexamethyldisilazane 15g, isopropanol 6.5g, insulation reaction 5h is added in polycondensation product.Stop after reaction anti-
It answers, cooling, discharging obtains high-temperaure coating agent.
(3) coating technique
Toluene 200g, the 4g of SILICONE COATING AGENT containing fluorophenyl and dibenzoyl peroxide (BPO) are sequentially added in a reservoir
0.1g, after mixing evenly, obtained dilution glue with glue spreader gluing, control glue-line on polyester film (300 microns of thickness)
With a thickness of 0.05 ~ 0.06mm.2min is dried after gluing at 90 DEG C, then 5 min of drying solidifies to obtain heat-resistant polyester at 150 DEG C
Composite material.
(4) bonding test
Measuring heat-resistant polyester composite material peel strength according to GB/T 2792-1998 is 29.8N(2.5cm).According to GB/T
17875-1999 measures the SILICONE COATING AGENT of heat-resistant polyester composite material, and compression resistant and oxidation are up to 72h at 325 DEG C, and 260 DEG C
It remains to successfully remove from metal surface after lower exposure.
The molecular structure of above-mentioned SILICONE COATING AGENT product is as follows:
Wherein, m=3~8；n =2~4；p=2~5；X=2~5；Y=4~10.
Fig. 1 is above-mentioned SILICONE COATING AGENT thermogravimetric curve figure.In figure, curve a is that organosilicon prepared by embodiment one applies
The thermal weight loss test result thermogravimetric curve of layer agent, b are the thermal weight loss test results of SILICONE COATING AGENT prepared by embodiment two
Thermogravimetric curve, c are the thermal weight loss test result thermogravimetric curves of SILICONE COATING AGENT prepared by embodiment three, and d is embodiment
The thermal weight loss test result thermogravimetric curve of the SILICONE COATING AGENT of four preparations.As can be seen that all SILICONE COATING AGENTs all have
There is good heat resistance.It is also seen that products of the present invention heat resistance is good from heat resistance test result, 10% is weightless
Temperature reaches 342 DEG C.
Comparative example one: phenethyl SILICONE COATING AGENT
(1) phenethyl silicone resin is synthesized
500mL three-necked flask is equipped with thermometer, reflux condensing tube and constant pressure dropping funnel, oil bath heating.It sequentially adds
Chloroplatinic acid catalyst 0.16g is added under nitrogen protection for 80g toluene and 33g styrene, stirring and dissolving.Heating is opened, is warming up to 80
After DEG C, 50g dichloromethylsilane is added dropwise, time for adding is controlled at 1 hour or so.Drip subsequent continuous insulation reaction 2 hours.
After reaction, solvent and unreacted dimethyl dichlorosilane (DMCS) is evaporated off, vacuum distillation collects 112 DEG C of fractions (3.75kPa), obtains nothing
Color transparency liquid product phenyl ethyl dimethyl chlorosilane 76g, it is 95.3% that gas-chromatography, which measures product purity, yield 91.6%.
By 9g tri-methyl-chlorosilane, 16g phenyl ethyl dimethyl chlorosilane and the positive silicic acid second of 63g in 250mL conical flask
Ester is uniformly mixed, and obtains mixed silanes, spare.
500mL three-necked flask is equipped with thermometer, reflux condensing tube and constant pressure dropping funnel, oil bath heating.First by 7g water and
The 6g concentrated sulfuric acid is carefully slowly keyed in 55g tetrahydrofuran, after heating makes mixture temperature rise to 72 DEG C, is added dropwise at a slow speed above-mentioned preparatory
The mixed silanes prepared, time for adding are controlled in 30 ~ 50min.Add subsequent continuous insulation reaction 6 hours.Stop reaction, reaction solution
First vacuum distillation removes coproduct ethanol and solvents tetrahydrofurane, and the temperature of distillation is 60 DEG C, vacuum degree 10mmHg, and distillation is extremely
Until no liquid distillates.Toluene extracts 3 times, the use of toluene amount is every time 30g.Combining extraction liquid, to distill water washing 5 times, often
It is secondary to use 15g distilled water.After washing, it is 6 hours dry to add 5g anhydrous sodium sulfate.It is filtered to remove desiccant, Yu Wendu
Distillation obtains the bulk solids product phenethyl silicone resin of 36g white under the conditions of being 0.5mmHg for 80 DEG C, vacuum degree.
(2) polycondensation reaction
250mL three-necked flask is equipped with thermometer, water segregator and reflux condensing tube, constant pressure addition funnel, oil bath heating.According to
107 glue 16.8g and 16g toluene of secondary addition, stirring are warming up to 80 DEG C, add 0.18g dibutyl tin dilaurate (DBTL).Logical nitrogen
Gas is added dropwise 0.13g dimethyl diethoxysilane and is dissolved in the solution in 2.5g toluene, and 30min is added, insulation reaction 3h.So
Afterwards, 22g phenethyl silicone resin is added and is dissolved in the solution in 25g toluene, increase temperature to 110 DEG C, reflux water-dividing reacts for 24 hours.
(3) it post-processes
Hexamethyldisilazane 0.12g, isopropanol 0.46g, insulation reaction 5h is added in polycondensation product.Stop after reaction
Reaction, cooling, discharging, obtains control sample SILICONE COATING AGENT stick.
(4) coating technique
Toluene 200g, phenethyl SILICONE COATING AGENT 4g and dibenzoyl peroxide (BPO) are sequentially added in a reservoir
0.1g, after mixing evenly, obtained dilution glue with glue spreader gluing, control glue-line on polyester film (500 microns of thickness)
With a thickness of 0.05 ~ 0.06mm.2min is dried after gluing at 90 DEG C, then at 150 DEG C 5 min of drying solidify to obtain polyester it is compound
Material.
(5) bonding test
Measuring polyester composite agent peel strength according to GB/T 2792-1998 is 30.8N(2.5cm).According to GB/T
17875-1999 measures the organic silicon coating of polyester composite, and compression resistant and oxidation are up to 72h at 325 DEG C, exposure at 260 DEG C
Glue-line 80% falls off afterwards, and part glue-line remains in metal surface, and remaining glue-line becomes fragile, and color is whitened, and stomata occurs in side contracting.It is right
It is as follows according to the molecular structure of SILICONE COATING AGENT product:
Wherein, m=3~9；n =2~4；p=2~5；X=2~5；Y=4~10.
Claims (10)
1. a kind of high temperature resistance polyester composite material, which is characterized in that the high temperature resistance polyester composite material include polyester base material with
And coated on the SILICONE COATING AGENT on polyester base material；
The chemical structural formula of the SILICONE COATING AGENT is as follows:
Wherein, m=5~20；N=1~5；P=1~8；X=0~6；Y=1~10.
2. high temperature resistance polyester composite material according to claim 1, which is characterized in that the high temperature resistance polyester composite material
Preparation method includes the following steps:
(1) activator solution is added dropwise in the mixture of 107 sol solutions and catalyst, it is molten that fluorine-containing phenyl polysiloxane is then added
Liquid, reflux water-dividing reaction, obtains polycondensation product；
(2) after mixing polycondensation product with curing agent, organic solvent, heat preservation curing obtains SILICONE COATING AGENT；
(3) by the mixture coating of SILICONE COATING AGENT, oxidant, diluent on polyester base material, drying, solidification obtain resistance to height
Warm polyester composite；
The chemical structural formula of the fluorine-containing phenyl polysiloxane are as follows:
Wherein, m=5~20；N=1~5；P=1~8.
3. high temperature resistance polyester composite material according to claim 2, which is characterized in that the activator, 107 peptizations, catalysis
Agent, fluorine-containing phenyl polysiloxane mass ratio be (0.005~0.05): 1: (0.005~0.06): (1~10)；The polycondensation product
Mass ratio with curing agent is (0.02~0.5): (0.02~0.3)；The quality of the SILICONE COATING AGENT, oxidant, solvent
Than for (1~3): 100: (0.04~0.06).
4. high temperature resistance polyester composite material according to claim 2, which is characterized in that solvent is virtue in the activator solution
Fragrant hydrocarbon solvent；Solvent is aromatic hydrocarbon solvent in 107 sol solutions；Solvent is aromatic hydrocarbon in the fluorine-containing phenyl polysiloxane solution
Class solvent；The organic solvent is isopropanol；The curing agent is hexamethyldisilazane；The catalyst is tin dilaurate two
Butyl tin；The activator is dimethyldimethoxysil,ne or dimethyl diethoxysilane；The oxidant is peroxide
Change dibenzoyl or peroxidating -2,4 dichloro benzene formyl.
5. high temperature resistance polyester composite material according to claim 2, which is characterized in that
In step (1), at 80 DEG C ~ 100 DEG C, catalyst is added in 107 sol solutions；Then under nitrogen protection, activation is added dropwise
Agent solution, is added dropwise to complete rear insulation reaction 1 ~ 6 hour；Then fluorine-containing phenyl polysiloxane solution is added, in 100 ~ 140 DEG C of reflux point
Water reacts 2 ~ 60h, obtains polycondensation product；
In step (2), the temperature for keeping the temperature curing is 100 ~ 140 DEG C, and the time is 1 ~ 6 hour；
In step (3), drying is to dry 2min at 90 DEG C, is cured as solidifying 5 min at 150 DEG C.
6. high temperature resistance polyester composite material according to claim 5, which is characterized in that the time that activator solution is added dropwise is
0.5 ~ 3 hour.
7. high temperature resistance polyester composite material according to claim 2, which is characterized in that the preparation of the fluorine-containing phenyl polysiloxane
Method the following steps are included:
(1) pentafluorostyrene is dissolved in aromatic hydrocarbon solvent, precious metal salt catalyst is added under nitrogen protection；Then in 50
Dimethyl dichlorosilane (DMCS) is added dropwise at~140 DEG C；It is added dropwise to complete rear insulation reaction 1 ~ 10 hour, prepares phenyl-pentafluoride ethyl dimethyl chloride silicon
Alkane；
(2) in organic solvent by water, inorganic acid dispersion, phenyl-pentafluoride ethyl dimethylchlorosilane is then added dropwise at 60~80 DEG C
With the mixture of ethyl orthosilicate, heat preservation is carried out a polycondensation 0.5~1 hour after being added dropwise to complete；Then trialkyl one is added dropwise again
The mixture of chlorosilane and ethyl orthosilicate, heat preservation carries out polycondensation reaction 1~6 hour again after being added dropwise to complete, and preparation contains fluorobenzene
Base silicone resin.
8. high temperature resistance polyester composite material according to claim 7, which is characterized in that pentafluorostyrene, precious metal salt, methyl
The mass ratio of dichlorosilane is 1: (0.003~0.006): (0.5~2)；Phenyl-pentafluoride ethyl dimethylchlorosilane and positive silicic acid second
In the mixture of ester, the mass ratio of phenyl-pentafluoride ethyl dimethylchlorosilane and ethyl orthosilicate is (1~6): (1~10)；Three hydrocarbon
In the mixture of one chlorosilane of base and ethyl orthosilicate, the mass ratio of one chlorosilane of trialkyl and ethyl orthosilicate is (1~3):
(1~10)；The precious metal salt is chloroplatinic acid；One chlorosilane of trialkyl is trim,ethylchlorosilane, one chlorine of dimethyl hydrogen-based
One of silane, one chlorosilane of dimethyl ethenyl, one chlorosilane of pheiiyldimetliyl；The inorganic acid is the concentrated sulfuric acid or dense
Hydrochloric acid.
9. high temperature resistance polyester composite material according to claim 7, which is characterized in that the time that dimethyl dichlorosilane (DMCS) is added dropwise is
0.5~5 hour；The time that the mixture of one chlorosilane of trialkyl and ethyl orthosilicate is added dropwise is 0.5 ~ 1 hour；Step (1) is anti-
After answering, reaction solution obtains phenyl-pentafluoride ethyl dimethylchlorosilane by being evaporated off, being evaporated under reduced pressure；Polycondensation is anti-again for step (2)
After answering, reaction solution is obtained through supercooling, vacuum distillation, liquid separation processing, extraction, distillation water washing, drying, filtering, distillation
Fluorine-containing phenyl polysiloxane.
10. fluorine-containing phenyl polysiloxane or SILICONE COATING AGENT are preparing the application in high temperature resistance polyester composite material；It is described to contain
The chemical structural formula of fluorophenyl silicone resin are as follows:
Wherein, m=5~20；N=1~5；P=1~8；
The chemical structural formula of the SILICONE COATING AGENT is as follows:
Wherein, m=5~20；N=1~5；P=1~8；X=0~6；Y=1~10.
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