CN106496565B - A kind of tackifier, preparation method and silicone rubber compound - Google Patents
A kind of tackifier, preparation method and silicone rubber compound Download PDFInfo
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- CN106496565B CN106496565B CN201611122767.7A CN201611122767A CN106496565B CN 106496565 B CN106496565 B CN 106496565B CN 201611122767 A CN201611122767 A CN 201611122767A CN 106496565 B CN106496565 B CN 106496565B
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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
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives 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; Adhesives based on derivatives of such polymers
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Abstract
This application provides a kind of tackifier with structure shown in formula (I), wherein R1Selected from methyl, ethyl or phenyl；R2For hydrogen；R3Selected from cyclopentenyl, cyclohexenyl group, 3- cyclohexenylethyl, 4- cyclohexenylethyl, 5- bicycloheptene base, 4- cyclo-octene base, 4- cyclo-octene base ethyl, 1,5- cyclo-octadiene base or norbornenylethyl；R4Selected from methyl methacrylate base, allyl methacrylate base or glycidyl methacrylate base；A, b, c are all larger than equal to 1, and 20≤a+b+c≤70.Tackifier of the invention can significantly improve the bond effect between silicon rubber and difficult tackifying resin substrate.
Description
Technical field
The present invention relates to binding material technical field more particularly to a kind of tackifier, preparation method and rubber composition
Object.
Background technique
Silicon rubber is because having high-low temperature resistant, weather-resistant, resistance to ozone, electrical isolation, resistance to combustion, nontoxic, corrosion-free and physiology
The excellent properties such as inertia and be widely applied in various fields, be used for example as medical and diving outfit breathing mask sealing
Circle, the gasket of various electric appliances (such as oven and micro-wave oven), automobile component such as spark plug high-voltage shield and other connectors it is close
Sealing.In this many application, silicon rubber is usually, the work such as sealing or protection bonding with metal base or resin base material
With, however, for usual silicone rubber, it is often poor to the caking property of substrate, it is easy to peel off from substrate.
Currently, generally passing through following three kinds of modes to improve silicon rubber to the caking property of substrate: (1) first in resin base
Material surface is coated with primary coat paint, and further coating silicon rubber makes its solidification, realizes the bonding of silicon rubber and substrate；(2) to silicon rubber
The molecular structure of glue itself improves, and improves its caking property；(3) tackifier are introduced into silicon rubber to improve silicon rubber and base
Caking property between material.Wherein, using the method for primary coat paint and modified silicon rubber molecular structure, complicated operation, and spends the time
It is longer, higher cost；And introduce tackifier method is simple, the operating time is shortened, is reduced costs, work is improved
Efficiency becomes the effective ways for improving silicon rubber and substrate caking property.
However, tackifier in the prior art are often only capable of improving silicon rubber and conventional thermoplastic resin's such as acrylic nitrile-butadiene
Styrene (ABS) resin, polyethylene (PE) resin, polypropylene (PP) resin, gathers to benzene two polycarbonate (PC) resin
Formic acid butanediol ester (PBT) resin, polyethylene terephthalate (PET) resin, nylon (PA) resin, aromatic polyamide
(aromatic series PA) resin, polyphenylene oxide (PPO) resin, polyphenylene sulfide (PPS) resin, polyimides (PI) resin, acrylic acid series tree
The caking property of rouge and polyurethane (PU) resin etc.；As the Chinese patent of Publication No. CN102675884B discloses a kind of silicon rubber
Composition by the polysiloxanes containing aromatic structure and other coupling agents and is used as tackifier and is added in silicon rubber, obtains
To composition can form the short time, and can be improved to carbonic ester as described above, polybutylene terephthalate (PBT),
The caking property of conventional thermoplastic resins' substrate such as polyethylene terephthalate and polyphenylene sulfide.But for some difficult viscous
Property resin base material such as glass fiber reinforced polyamide (glass PA), polyetherimide resin (PEI) and polyphenylsulfone tree
Rouge (PPSU) etc., bond effect can not be generated or improve by introducing above-mentioned tackifier.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of tackifier, preparation method and silicone rubber compound are used
Tackifier of the invention can improve the caking property of silicon rubber and difficult tackifying resin substrate.
The present invention provides a kind of tackifier, have structure shown in formula (I):
Wherein,
R1Selected from methyl, ethyl or phenyl；
R2For hydrogen；
R3Selected from cyclopentenyl, cyclohexenyl group, 3- cyclohexenylethyl, 4- cyclohexenylethyl, 5- bicycloheptene base, 4-
Cyclo-octene base, 4- cyclo-octene base ethyl, 1,5- cyclo-octadiene base or norbornenylethyl；
R4Selected from methyl methacrylate base, allyl methacrylate base or glycidyl methacrylate base；
A, b, c are all larger than equal to 1, and 20≤a+b+c≤70.
Preferably, 20≤a≤55,1≤b≤20,1≤c≤15.
Preferably, a > b >=c.
The present invention also provides a kind of preparation methods of tackifier described in above-mentioned technical proposal, comprising the following steps:
A organic hydrogen polysiloxanes are mixed with the first solvent), obtain the first mixture；
B) cycloolefin, esters, catalyst and the second solvent are mixed, obtain the second mixture；
C the first mixture is mixed with the second mixture), is reacted, tackifier are obtained；
The step A) in, the organic hydrogen polysiloxanes have structure shown in formula (II):
Wherein, R1Selected from methyl, ethyl or phenyl；R2For hydrogen；20≤n≤70；
The step B) in, the cycloolefin be cyclopentene, cyclohexene, 3- vinylcyclohexene, 4 vinyl cyclohexene,
5- bicycloheptene, 4- cyclo-octene, 4- vinyl cyclo-octene, 1,5- cyclo-octadiene or vinyl norbornene；The esters are first
Base methyl acrylate, allyl methacrylate or glycidyl methacrylate.
Preferably, first solvent is one or more of toluene, hexamethylene and dimethylbenzene；
Second solvent is one or more of toluene, hexamethylene and dimethylbenzene.
Preferably, the catalyst is one in Speier catalyst, Karstedt catalyst and Lamoreaux catalyst
Kind is several.
Preferably, the dosage of the catalyst be the organic hydrogen polysiloxanes, cycloolefin and esters gross mass 5~
30ppm。
Preferably, the step C) in, the temperature of the reaction is 30~100 DEG C.
Preferably, the step C) in, after the first mixture is mixed, reacted with the second mixture, after further including progress
Processing, after the post-processing, obtains tackifier；
The post-processing removes catalyst including the use of activated carbon adsorption and removes solvent under the conditions of vacuum decompression.
The present invention also provides a kind of silicone rubber compound, including tackifier described in silicon rubber and above-mentioned technical proposal or
Tackifier made from preparation method described in above-mentioned technical proposal.
Compared with prior art, tackifier provided by the invention breach common tackifier and are only capable of improving conventional interchangeable heat
The caking property of plastic resin substrate and the limitation that cannot bond difficult tackifying resin substrate can significantly improve silicon rubber and difficulty viscosity
The caking property of resin base material such as glass fiber reinforced polyamide, polyetherimide resin and polyphenylene sulphone resin etc., also
It will not influence the other performance of silicon rubber, there is preferable stability.The present invention also provides a kind of preparation method of tackifier,
This method mild condition, simple, strong operability are easy to industrialized production.It include the thickening the present invention also provides one kind
The silicone rubber compound of agent has good bond effect to difficult tackifying resin substrate.
Specific embodiment
The present invention provides a kind of tackifier, have structure shown in formula (I):
Wherein,
R1Selected from methyl, ethyl or phenyl；
R2For hydrogen；
R3Selected from cyclopentenyl, cyclohexenyl group, 3- cyclohexenylethyl, 4- cyclohexenylethyl, 5- bicycloheptene base, 4-
Cyclo-octene base, 4- cyclo-octene base ethyl, 1,5- cyclo-octadiene base or norbornenylethyl；
R4Selected from methyl methacrylate base, allyl methacrylate base or glycidyl methacrylate base；
A, b, c are all larger than equal to 1, and 20≤a+b+c≤70.
Tackifier provided by the invention have formula (I) structure, can enhance the cementation between silicon rubber and substrate interface,
It is obviously improved the bond effect of difficult tackifying resin substrate, and will not influence the other performance of silicon rubber, there is preferable stability.
In tackifier shown in formula (I) provided by the invention, R1Selected from methyl, ethyl or phenyl, preferably methyl.R2For hydrogen.
R3Selected from cyclopentenyl, cyclohexenyl group, 3- cyclohexenylethyl, 4- cyclohexenylethyl, 5- bicycloheptene base, 4-
Cyclo-octene base, 4- cyclo-octene base ethyl, 1,5- cyclo-octadiene base or norbornenylethyl, preferably 4- cyclohexenylethyl,
4- cyclo-octene base ethyl, 1,5- cyclo-octadiene base or norbornenylethyl.
R4Selected from methyl methacrylate base, allyl methacrylate base or glycidyl methacrylate base.
A, b, c are all larger than equal to 1, and 20≤a+b+c≤70, preferably 25≤a+b+c≤65, and more preferable 30≤a+b+c≤
60。
In the present invention, 20≤a≤55, preferably 20≤a≤50.1≤b≤20, preferably 3≤b≤15.1≤c≤15, preferably 3
≤c≤10。
In the present invention, preferably a > b >=c, in certain embodiments, a > b=c.
In the present invention, the refractive index of the tackifier is preferably 1.44~1.47, and more preferably 1.45~1.46.
The present invention also provides a kind of preparation methods of above-mentioned tackifier, comprising the following steps:
A organic hydrogen polysiloxanes are mixed with the first solvent), obtain the first mixture；
B) cycloolefin, esters, catalyst and the second solvent are mixed, obtain the second mixture；
C the first mixture is mixed with the second mixture), is reacted, tackifier are obtained；
The step A) in, the organic hydrogen polysiloxanes have structure shown in formula (II):
Wherein, R1Selected from methyl, ethyl or phenyl；R2For hydrogen；20≤n≤70；
The step B) in, the cycloolefin be cyclopentene, cyclohexene, 3- vinylcyclohexene, 4 vinyl cyclohexene,
5- bicycloheptene, 4- cyclo-octene, 4- vinyl cyclo-octene, 1,5- cyclo-octadiene base or vinyl norbornene；The esters are
Methyl methacrylate, allyl methacrylate or glycidyl methacrylate.
According to the present invention, organic hydrogen polysiloxanes are mixed with the first solvent, obtain the first mixture.
In the present invention, the organic hydrogen polysiloxanes have structure shown in formula (II):
Wherein, R1Selected from methyl, ethyl or phenyl, preferably methyl.R2For hydrogen.20≤n≤70, preferably 25≤n≤65,
More preferable 30≤n≤60.
In the present invention, first solvent is preferably one or more of toluene, hexamethylene and dimethylbenzene.The present invention couple
The source of first solvent is not particularly limited, and is general commercially available product.To by organic hydrogen polysiloxanes and first in the present invention
The mode of solvent mixing is not particularly limited, and can be uniformly mixed the two.
According to the present invention, cycloolefin, esters, catalyst and the second solvent are mixed, the second mixture is obtained.
In the present invention, the cycloolefin be preferably cyclopentene, cyclohexene, 3- vinylcyclohexene, 4 vinyl cyclohexene,
5- bicycloheptene, 4- cyclo-octene, 4- vinyl cyclo-octene, 1,5- cyclo-octadiene or vinyl norbornene, more preferably 4- second
Alkenyl cyclohexene, 4- vinyl cyclo-octene, 1,5- cyclo-octadiene or vinyl norbornene.The present invention carrys out the cycloolefin
Source is not particularly limited, and is general commercially available product.
In the present invention, the esters are preferably methyl methacrylate, allyl methacrylate or methacrylic acid contracting
Water glyceride.The present invention is not particularly limited the source of the esters, is general commercially available product.
In the present invention, the catalyst is preferably Speier catalyst, Karstedt catalyst and Lamoreaux catalyst
Middle one or more.The dosage of the catalyst is preferably the 5 of the gross mass of the organic hydrogen polysiloxanes, cycloolefin and esters
Ratio 5~the 30mg/kg, more preferably 10~20ppm of~30ppm, i.e. catalyst and all reactant gross mass.The catalyst
Mass concentration be preferably 0.2%~1.0%.The present invention is not particularly limited the source of catalyst, is for general commercially available product
It can.
In the present invention, second solvent is preferably one or more of toluene, hexamethylene and dimethylbenzene, the present invention couple
The source of second solvent is not particularly limited, and is general commercially available product.In the present invention to by cycloolefin, esters, catalyst and
The mode of second solvent mixing is not particularly limited, and can be mixed uniformly.
In the present invention, the gross mass of first solvent and the second solvent is preferably the organic hydrogen polysiloxanes, cyclenes
0.5~2 times of the gross mass of hydrocarbon and esters.Dosage and second mixture of the present invention to the first solvent in the first mixture
In the dosage of the second solvent be not particularly limited, a conventional distribution regulation is carried out according to the molten object of institute, reactant dissolution can be made to obtain
Homogeneous solution.
The present invention can be obtained simultaneously to obtaining the first mixture and obtain the sequence of the second mixture to be not particularly limited
Or it successively obtains.
According to the present invention, after obtaining the first mixture and the second mixture, the first mixture and the second mixture are mixed
It closes, reaction, obtains tackifier.
In the present invention, the mode that the first mixture is mixed with the second mixture is not particularly limited, in some embodiments
In, the second mixture can be added drop-wise in the first mixture.In the present invention, the temperature of the reaction is preferably 30~100 DEG C, more
Preferably 40~100 DEG C, further preferably 60~90 DEG C.The time of the reaction is preferably 2~4h, by the first mixture and
After the reaction of second mixture, tackifier shown in formula (I) are obtained.
For example, in some embodiments, organic hydrogen polysiloxanes and cycloolefin, ester reaction are prepared as follows
Tackifier:
Wherein, R1For methyl, ethyl or phenyl.
In the present invention, after the first mixture is mixed, reacted with the second mixture, after preferably being carried out to reaction product
Reason, obtains tackifier after post-processing.In the present invention, it is described post-processing preferably include using activated carbon adsorption remove catalyst and
Solvent is removed under the conditions of vacuum decompression.
In the present invention, after the first mixture is mixed, reacted with the second mixture, removed preferably by activated carbon adsorption
Catalyst in reaction product.In the present invention, the specific surface area of the active carbon is preferably 500~1700m2/ g, more preferably
800~1600m2/ g, further preferably 1000~1500m2/g.In the present invention, the dosage of the active carbon is preferably described to be urged
50~100 times of agent quality.It is preferably 2~5h using the time that active carbon adsorbs reaction product.The present invention is preferably in room
Active carbon Removal of catalyst is utilized under the conditions of temperature.The present invention is not particularly limited the source of the active carbon, is general commercially available
Product, such as in certain embodiments, active carbon can be the ZQ-248 active carbon purchased from great achievement water process Co., Ltd.
In the present invention, after Removal of catalyst, solvent is further preferably removed under the conditions of vacuum decompression.In the present invention,
The vacuum degree of the vacuum decompression is preferably 20~80mmHg.In the present invention, the removing solvent is preferably 70~150 in material temperature
It carries out at DEG C, is more preferably carried out at 80~140 DEG C.The present invention obtains colorless and transparent increasing preferably after the post-processing
Stick.
Preparation method mild condition provided by the invention, simple, strong operability are easy to industrialized production.
The present invention also provides a kind of silicone rubber compound, the tackifier that are provided including silicon rubber and above-mentioned technical proposal or
According to tackifier made from above-mentioned preparation method.In the present invention, the type of the silicon rubber is not particularly limited, and is in this field
Conventional silicone rubber can be such as conventional add-on type liquid silicon rubber.The source of the silicon rubber is not particularly limited, and can be
Commercially available or self-control.In the present invention, the ratio of the silicon rubber and tackifier is not particularly limited, according to conventional in the art mixed
Composition and division in a proportion example executes.
Silicon rubber is added to (as routine adds by tackifier of the invention or according to tackifier made from above-mentioned preparation method
Molding liquid silicon rubber) in, it can be realized silicon rubber to such as glass fiber reinforced polyamide, polyetherimide resin and gather
The hardly possible tackifying resin substrate such as phenylene sulphone resin it is well-bonded.
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are only further explanation the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
Embodiment 1
Toluene is packed into the 500mL four-hole boiling flask equipped with reflux condenser, thermometer, dropping funel and mechanical agitator
(113.1g) and organic hydrogen polysiloxanes (113.1g, 0.05mol), are heated to 80 DEG C, in vinyl norbornene is added dropwise in 30min
Alkene (30.05g, 0.25mol), methyl methacrylate (25.03g, 0.25mol), Karstedt catalyst (0.34g, concentration
0.5%) with the mixture of toluene (55.08g), after being added dropwise, isothermal reaction 3h, obtains reaction product at 80 DEG C.It will be anti-
It answers product stirring to be cooled to room temperature, the active carbon (22.1g) for toasting 3h through 120 DEG C is added, stir 2h, filtering；Again by gains
Material 120 DEG C, vacuum degree be 30mmHg under conditions of remove solvent, obtain 137.9g it is colorless and transparent with formula (a) structure
Tackifier；
The bond effect of gained formula (a) tackifier is tested, test method is as follows: by 100 parts of silicon rubber and 1 part of formula
(a) tackifier mix, and stir evenly at room temperature, obtain silicone rubber compound.By gained silicone rubber compound temperature be 120
DEG C, pressure be 100MPa under conditions of, respectively with glass fiber reinforced polyamide substrate (glass PA), polyetherimide tree
Rouge (PEI) substrate, polyphenylene sulphone resin (PPSU) substrate are molded 200s, test silicon rubber and various resin base materials after cooling
Adhesive strength, as a result referring to table 1.
Wherein, silicon rubber used can be prepared as follows: to the diformazan by dimethyl ethenyl first siloxane blocking
Addition has being sealed by trimethylsiloxy for vinyl in based polysiloxane (25 DEG C of viscosity be 30000mPas, 65 parts)
Dimethyl polysiloxane (ethylene base value 0.096mmol/g, 5 parts), fumed silica (the BET specific surface area 200m at end2/ g,
25 parts, day Bender mountain QS-20), methylsilazane (6 parts), vinyl silazane (2.5 parts) and water (0.6 part), kneader/
It is uniformly mixed in mixer and further mixes 3h in 150 DEG C of heating, obtain silicone rubber precursor.It is added with into silicone rubber precursor
Tetramethyl divinyl siloxane solution (the concentration of machine hydrogen polysiloxanes (SiH content 7mmol/g, 1.8 parts), chloroplatinic acid
0.25wt%, 0.5 part) and ethynylcyclohexanol ethanol solution (concentration 10wt%, 0.8 part), after uniformly mixing 20min, obtain
To silicon rubber.
Embodiment 2
Toluene is packed into the 1L four-hole boiling flask equipped with reflux condenser, thermometer, dropping funel and mechanical agitator
(304.2g) and organic hydrogen polysiloxanes (304.2g, 0.1mol), are heated to 70 DEG C, in vinyl norbornene is added dropwise in 1h
(48.08g, 0.4mol), allyl methacrylate (50.46g, 0.4mol), Karstedt catalyst (0.64g, concentration
0.5%) with the mixture of toluene (98.54g), after being added dropwise, isothermal reaction 3h, obtains reaction product at 70 DEG C.It will be anti-
It answers product stirring to be cooled to room temperature, the active carbon (41.6g) for toasting 3h through 150 DEG C is added, stir 3h, filtering；Again by gains
Material 130 DEG C, vacuum degree be 40mmHg under conditions of remove solvent, obtain 342.33g it is colorless and transparent with formula (b) structure
Tackifier；
Test formula (b) tackifier are to the bond effect between silicon rubber and difficult tackifying resin substrate according to the method for embodiment 1,
As a result referring to table 1.
Embodiment 3
Toluene is packed into the 1L four-hole boiling flask equipped with reflux condenser, thermometer, dropping funel and mechanical agitator
(272.16g) and organic hydrogen polysiloxanes (272.16g, 0.08mol), are heated to 70 DEG C, in vinyl norbornene is added dropwise in 1h
Alkene (76.92g, 0.64mol), glycidyl methacrylate (90.98g, 0.64mol), Karstedt catalyst (1.06g,
Concentration 0.5%) with the mixture of toluene (167.9g), after being added dropwise, isothermal reaction 3h, obtains reaction product at 70 DEG C.
Reaction product stirring is cooled to room temperature, the active carbon (68.9g) for toasting 3h through 150 DEG C is added, stirs 3h, filtering；Again by institute
Material 140 DEG C, vacuum degree be 40mmHg under conditions of remove solvent, obtain 364.25g it is colorless and transparent have formula (c) knot
The tackifier of structure；
Test formula (c) tackifier are to the bond effect between silicon rubber and difficult tackifying resin substrate according to the method for embodiment 1,
As a result referring to table 1.
Embodiment 4
Hexamethylene is packed into the 500mL four-hole boiling flask equipped with reflux condenser, thermometer, dropping funel and mechanical agitator
Alkane (122.1g) and organic hydrogen polysiloxanes (122.1g, 0.05mol), are heated to 90 DEG C, in dropwise addition 4- ethylene basic ring in 30min
Hexene (54.09g, 0.5mol), methyl methacrylate (25.03g, 0.25mol), Speier catalyst (0.42g, concentration
0.5%) with the mixture of toluene (79.12g), after being added dropwise, isothermal reaction 3h, obtains reaction product at 90 DEG C.It will be anti-
It answers product stirring to be cooled to room temperature, the active carbon (27.3g) for toasting 3h through 120 DEG C is added, stir 2h, filtering；Again by gains
Material 120 DEG C, vacuum degree be 30mmHg under conditions of remove solvent, obtain 151.6g it is colorless and transparent with formula (d) structure
Tackifier；
Test formula (d) tackifier are to the bond effect between silicon rubber and difficult tackifying resin substrate according to the method for embodiment 1,
As a result referring to table 1.
Embodiment 5
Dimethylbenzene is packed into the 1L four-hole boiling flask equipped with reflux condenser, thermometer, dropping funel and mechanical agitator
(274.2g) and organic hydrogen polysiloxanes (274.2g, 0.1mol), are heated to 60 DEG C, in dropwise addition 4- vinyl cyclo-octene in 1h
(122.6g, 0.9mol), glycidyl methacrylate (85.29g, 0.6mol), Lamoreaux catalyst (0.67g, it is dense
Degree is 0.5%) with the mixture of toluene (207.89g), and after being added dropwise, isothermal reaction 3h, obtains reaction product at 60 DEG C.It will
Reaction product stirs cooling room temperature, and the active carbon (43.87g) that 3h is toasted through 150 DEG C is added, and stirs 2h, filtering；Again by gains
Material 140 DEG C, vacuum degree be 40mmHg under conditions of remove solvent, obtain 376.9g it is colorless and transparent with formula (e) structure
Tackifier；
Test formula (e) tackifier are to the bond effect between silicon rubber and difficult tackifying resin substrate according to the method for embodiment 1,
As a result referring to table 1.
Comparative example 1
Toluene is packed into the 1L four-hole boiling flask equipped with reflux condenser, thermometer, dropping funel and mechanical agitator
(221.34g) and organic hydrogen polysiloxanes (221.34g, 0.07mol), are heated to 80 DEG C, in dropwise addition Alpha-Methyl benzene second in 40min
Alkene (82.6g, 0.7mol), allyl glycidyl ether (79.8g, 0.7mol), Karstedt catalyst (0.77g, concentration
0.5%) with the mixture of toluene (162.4g), after being added dropwise, isothermal reaction 3h, obtains reaction product at 80 DEG C.It will be anti-
It answers product to stir cooling room temperature, the active carbon (50.1g) for toasting 3h through 150 DEG C is added, stir 2h, filtering；Again by resulting material
In 120 DEG C, vacuum degree to remove solvent under conditions of 40mmHg, the colorless and transparent increasing with formula (f) structure of 242.5g is obtained
Stick；
Test formula (f) tackifier are to the bond effect between silicon rubber and difficult tackifying resin substrate according to the method for embodiment 1,
As a result referring to table 1.
Comparative example 2
Toluene is packed into the 1L four-hole boiling flask equipped with reflux condenser, thermometer, dropping funel and mechanical agitator
The organic hydrogen polysiloxanes (330.6g, 0.1mol) that (330.6g) and phenyl replace, are heated to 80 DEG C, in second is added dropwise in 50min
Alkenyl trimethoxy silane (88.8g, 0.6mol), Karstedt catalyst (0.84g, concentration 0.5%) and toluene (88.8g)
Mixture, after being added dropwise, isothermal reaction 3h, obtains reaction product at 80 DEG C.Reaction product is stirred into cooling room temperature, is added
The active carbon (54.5g) of 3h is toasted through 150 DEG C, stirs 2h, filtering；It is again 30mmHg's in 120 DEG C, vacuum degree by resulting material
Under the conditions of remove solvent, obtain the colorless and transparent tackifier with formula (g) structure of 269.8g；
Test formula (g) tackifier are to the bond effect between silicon rubber and difficult tackifying resin substrate according to the method for embodiment 1,
As a result referring to table 1.
The bond effect of the tackifier of the tackifier and comparative example 1~2 of 1 the embodiment of the present application 1~5 of table
Wherein, each symbol meaning is as follows:
×: cohesional failure=0% (removing)；
+: 30% >=cohesional failure > 0%；
++: 60% >=cohesional failure > 30%；
+++: 90% >=cohesional failure > 60%；
++++: cohesional failure > 90%.
As seen from the above embodiment, tackifier provided by the invention can significantly improve silicon rubber and difficult tackifying resin substrate
Between bond effect, keep silicon rubber and difficult tackifying resin substrate well-bonded, broken conventional tackifiers be only capable of improving it is conventional logical
The limitation of difficult tackifying resin substrate cannot be bonded with the caking property of thermoplastic resin substrate.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.To these embodiments
A variety of modifications will be readily apparent to those skilled in the art, the general principles defined herein can be with
Without departing from the spirit or scope of the present invention, it realizes in other embodiments.Therefore, the present invention will not be limited
In the embodiments shown herein, and it is to fit to widest model consistent with the principles and novel features disclosed in this article
It encloses.
Claims (10)
1. a kind of tackifier, which is characterized in that have structure shown in formula (I):
Formula (I)；
Wherein,
R1Selected from methyl, ethyl or phenyl；
R2For hydrogen；
R3Selected from 3- cyclohexenylethyl, 4- cyclohexenylethyl, 4- cyclo-octene base ethyl or norbornenylethyl；
R4Selected from 2- methoxycarbonyl group-propyl, propyl methacrylate base or 2- glycidol ester group-propyl；
A, b, c are all larger than equal to 1, and 20≤a+b+c≤70.
2. tackifier according to claim 1, which is characterized in that 20≤a≤55,1≤b≤20,1≤c≤15.
3. tackifier according to claim 1 or 2, which is characterized in that a > b >=c.
4. a kind of preparation method of tackifier as claimed in any one of claims 1 to 3, which is characterized in that including following step
It is rapid:
A organic hydrogen polysiloxanes are mixed with the first solvent), obtain the first mixture；
B) cycloolefin, esters, catalyst and the second solvent are mixed, obtain the second mixture；
C the first mixture is mixed with the second mixture), is reacted, tackifier are obtained；
The step A) in, the organic hydrogen polysiloxanes have structure shown in formula (II):
Formula (II)；
Wherein, R1Selected from methyl, ethyl or phenyl；R2For hydrogen；20≤n≤70；
The step B) in, the cycloolefin is 3- vinylcyclohexene, 4 vinyl cyclohexene, 4- vinyl cyclo-octene or second
Alkenyl norbornene；The esters are methyl methacrylate, allyl methacrylate or glycidyl methacrylate.
5. the preparation method according to claim 4, which is characterized in that first solvent is toluene, hexamethylene and diformazan
One or more of benzene；
Second solvent is one or more of toluene, hexamethylene and dimethylbenzene.
6. the preparation method according to claim 4, which is characterized in that the catalyst be selected from Speier catalyst,
It is one or more of in Karstedt catalyst and Lamoreaux catalyst.
7. the preparation method according to claim 4 or 6, which is characterized in that the dosage of the catalyst is organic hydrogen
5 ~ 30ppm of the gross mass of polysiloxanes, cycloolefin and esters.
8. the preparation method according to claim 4, which is characterized in that the step C) in, the temperature of the reaction is 30 ~
100℃。
9. the preparation method according to claim 4 or 8, which is characterized in that the step C) in, by the first mixture and
After the mixing of two mixtures, reaction, further includes being post-processed, after the post-processing, obtain tackifier；
The post-processing removes catalyst including the use of activated carbon adsorption and removes solvent under the conditions of vacuum decompression.
10. a kind of silicone rubber compound, which is characterized in that including silicon rubber and thickening claimed in any one of claims 1 to 3
Tackifier made from preparation method described in any one of agent or claim 4 ~ 9.
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| CN111518314B (en) * | 2019-12-26 | 2021-12-07 | 江西贝特利新材料有限公司 | Tackifier, preparation method thereof and silicone rubber composition |
| CN111393598B (en) * | 2020-03-27 | 2022-03-22 | 无锡市百合花胶粘剂厂有限公司 | Primer for addition type organic silicon rubber and preparation method thereof |
| CN115322740B (en) * | 2022-08-26 | 2023-07-11 | 昆山石梅新材料科技有限公司 | Ultraviolet light curing pressure-sensitive adhesive and preparation method thereof |
| CN115785448B (en) * | 2022-11-28 | 2023-10-17 | 江西贝特利新材料有限公司 | Tackifier, preparation method thereof and silicone rubber composition |
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| CN103351467A (en) * | 2013-07-18 | 2013-10-16 | 东莞市贝特利新材料有限公司 | Addition type liquid silicone rubber bonding accelerant and preparation method and application thereof |
| CN104892942A (en) * | 2015-06-04 | 2015-09-09 | 成都拓利化工实业有限公司 | Tackifier for addition-type organic silicon rubber and preparation method thereof |
| CN104892945A (en) * | 2015-06-06 | 2015-09-09 | 深圳市富达瑞有机硅材料有限公司 | Organic silicon rubber composite tackifier and preparation method thereof |
| CN105400446A (en) * | 2015-12-18 | 2016-03-16 | 东莞市贝特利新材料有限公司 | Tackifier for high-refractive index LED liquid casting glue and preparation method thereof |
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| CN103351467A (en) * | 2013-07-18 | 2013-10-16 | 东莞市贝特利新材料有限公司 | Addition type liquid silicone rubber bonding accelerant and preparation method and application thereof |
| CN104892942A (en) * | 2015-06-04 | 2015-09-09 | 成都拓利化工实业有限公司 | Tackifier for addition-type organic silicon rubber and preparation method thereof |
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