CN104694057B - A kind of wall anti-disconnected acrylate pressure-sensitive adhesive and preparation method thereof - Google Patents
A kind of wall anti-disconnected acrylate pressure-sensitive adhesive and preparation method thereof Download PDFInfo
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- CN104694057B CN104694057B CN201510083098.6A CN201510083098A CN104694057B CN 104694057 B CN104694057 B CN 104694057B CN 201510083098 A CN201510083098 A CN 201510083098A CN 104694057 B CN104694057 B CN 104694057B
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Abstract
The invention provides a kind of wall anti-disconnected acrylate pressure-sensitive adhesive and preparation method thereof, the wall is with anti-disconnected acrylate pressure-sensitive adhesive mainly by soft monomer, hard monomer and function monomer copolymerization form, function monomer is acrylic acid PolyTHF ester and the acrylic acid of pyridine 2, acrylic acid PolyTHF ester has the Long carbon chain of ehter bond, it is flexible relatively good, the tensile elongation of pressure sensitive adhesive can be significantly improved, the acrylic acid of pyridine 2 can be formed with the Fe elements in wall and is coordinated, enhancing and the bonding force of wall, therefore, the wall has bonding strength height with anti-disconnected acrylate pressure-sensitive adhesive, strong adsorption force, good weatherability, the advantages that peel strength height and high elongation at break, it can be very good to be applied to the bonding with wall.
Description
Technical field
The present invention relates to a kind of Acrylate pressure sensitive agent and preparation method thereof, the anti-disconnected acrylic acid of more particularly to a kind of wall
Ester pressure-sensitive and preparation method thereof.
Background technology
Pressure sensitive adhesive is to presser sensor, is not required to heat, is not required to larger pressure, need to only refer to touch pressure can be achieved with bonding one
Kind adhesive.It is characterized in viscous easy, that takes off is not difficult, and shells without damaging, glue-line will not dry up in a long time, therefore pressure sensitive adhesive
Also referred to as adhesive sticker.The product of pressure sensitive adhesive is widely used in each field at present.Wherein Acrylic Pressure Sensitive Adhesive is pressure-sensitive
A major class in glue, its polymer have excellent weatherability, and ultraviolet resistance, heat-resisting, water-fast, chemical resistance is also excellent, and color and luster is saturating
It is bright, it is good with fastness, thus be rapidly developed in recent years.
At present, state's inner wall is relatively low with the adhesion strength between pressure sensitive adhesive generally existing pressure sensitive adhesive and wall base material, easily
The problems such as coming off and being easily broken off in drawing process.The presence of problems, brought to wall with the application of pressure sensitive adhesive very big
Inconvenience, while also constrain the development and application of wall pressure sensitive adhesive, and easily cause the wave of material in actual applications
Take and unnecessary economic loss.Therefore, people it is highly desirable to obtain a kind of adhesion strength high, and Resisting fractre intensity it is high and other
The wall pressure sensitive adhesive of function admirable.
The present invention is exactly in view of the above-mentioned problems, a kind of adhesion strength height has been made by the way of copolymerization, and Resisting fractre is strong
The wall pressure sensitive adhesive spent.Raw material needed for the product is easy to get, and simple production process, production cost is low, and accessory substance is few, efficiency
Height, be advantageous to industrialized production.Meanwhile the product can be widely applied to the fields such as construction material and interior decoration, therefore to people
Life benefit and economic benefit can produce active influence.
The content of the invention
It is an object of the invention to provide a kind of wall anti-disconnected acrylate pressure-sensitive adhesive and preparation method thereof, the wall is used
Anti- disconnected acrylate pressure-sensitive adhesive is mainly formed by the copolymerization of soft monomer, hard monomer and function monomer, and function monomer is acrylic acid poly- four
Hydrogen furans ester and pyridine -2- acrylic acid, acrylic acid PolyTHF ester have the Long carbon chain of ehter bond, relatively good, the Ke Yixian of flexibility
The tensile elongation for improving pressure sensitive adhesive is write, pyridine -2- acrylic acid can be formed with the Fe elements in wall and is coordinated, enhancing and wall
Bonding force, therefore, the wall has bonding strength height, strong adsorption force, good weatherability, stripping with anti-disconnected acrylate pressure-sensitive adhesive
The advantages that from intensity height and high elongation at break, it can be very good to be applied to the bonding with wall.
The anti-disconnected acrylate pressure-sensitive adhesive of a kind of wall of the present invention, mainly by soft monomer, hard monomer and function monomer
Copolymerization forms, and described function monomer is acrylic acid PolyTHF ester and pyridine -2- acrylic acid, acrylic acid PolyTHF ester
Molecular structural formula be：
Wherein n=3~10；
The anti-disconnected acrylate pressure-sensitive adhesive of wall use is not broken in the case of stretching 300%, and 180 ° of separation strengths are
2.0~4.0 pounds/25mm.
A kind of wall as described above is 8000~300000 with the number-average molecular weight of anti-disconnected acrylate pressure-sensitive adhesive.
A kind of wall as described above is also added into polymerizable wetting agent with anti-disconnected acrylate pressure-sensitive adhesive, and described can
Polymeric wetting agent is the mono-quaternaries cationic surfactant containing carbon-carbon double bond or the sun of the bi-quaternary ammonium salt containing carbon-carbon double bond
Ionic surface active agent.
A kind of wall preparation method of anti-disconnected acrylate pressure-sensitive adhesive, is made up of the raw material below in terms of parts by weight：
The soft monomer, it is different pungent for ethyl acrylate, butyl acrylate, acrylic acid-2-ethyl caproite, methacrylic acid
One kind or wherein several combinations in ester, lauryl methacrylate；
The hard monomer, it is one kind in acrylonitrile, acrylamide, styrene, methyl methacrylate, methyl acrylate
Or wherein several combination；
The function monomer, it is acrylic acid PolyTHF ester and pyridine -2- acrylic acid, wherein acrylic acid PolyTHF
The mass ratio of ester and pyridine -2- acrylic acid is 6~7:3；Acrylic acid PolyTHF ester has the Long carbon chain of ehter bond, and flexibility is relatively
It is good, the tensile elongation of pressure sensitive adhesive can be significantly improved；Due to containing the elements such as Ca, Al, Fe, pyridine -2- third in wall base material
The nitrogen in pyridine ring in acrylic monomer can be formed with the ferro element in wall base material to be coordinated, thus can greatly be carried
The adhesion strength of pressure-sensitive glue and wall；Under conditions of the mass ratio, the combination property of obtained pressure sensitive adhesive is most excellent.
The preparation of acrylic acid PolyTHF ester；
PTMG is dissolved in dichloromethane, is then added drop-wise in propylene isoxazolecarboxylic acid and reacts, generation third
Olefin(e) acid PolyTHF ester；
Prepare wall is with the process conditions of anti-disconnected acrylate pressure-sensitive adhesive：
Soft monomer, hard monomer and function monomer are dissolved in ethyl acetate by above-mentioned raw materials formula, are well mixed, then
The 10~20% of mixture gross mass are added in reactor, and described initiator is added dropwise, is heated to 70~85 DEG C of beginnings
Remaining said mixture and initiator, are then added drop-wise in reactor, were added dropwise to complete in 1~4 hour by reaction；Insulation 1
~2 hours, room temperature is then cooled to, adds crosslinking agent stirring, then discharging, obtains described wall with anti-disconnected acrylate pressure
Quick glue.
A kind of preparation method of the anti-disconnected acrylate pressure-sensitive adhesive of wall according to claim 4, it is characterised in that
The number-average molecular weight of PTMG is 600~2000；PTMG is dissolved in dense in dichloromethane
Spend for 20~30wt%；The mol ratio of PTMG and propylene isoxazolecarboxylic acid is 1~1.3:1；Reaction temperature be 10~
30 DEG C, 2~3h of reaction time；With triethylamine come caused hydrogen chloride gas, triethylamine during absorbing reaction in course of reaction
Mol ratio with propylene isoxazolecarboxylic acid is 1:1；Reaction product is through extract and separate, vacuum distillation and vacuum drying.
A kind of wall as described above preparation method of anti-disconnected acrylate pressure-sensitive adhesive, described initiator is azo two
Isobutyronitrile or benzoyl peroxide.
A kind of wall as described above preparation method of anti-disconnected acrylate pressure-sensitive adhesive, described crosslinking agent is more isocyanides
Acid esters, specially toluene di-isocyanate(TDI), methyl diphenylene diisocyanate or 1, hexamethylene-diisocyanate.
A kind of wall use as described above resists the preparation method of disconnected acrylate pressure-sensitive adhesive, and parts by weight are also added into raw material
Number is 1~3 polymerizable wetting agent, and described polymerizable wetting agent is the mono-quaternaries cationic surface work containing carbon-carbon double bond
Property agent or the bis-quaternary ammonium salt cationic surfactant containing carbon-carbon double bond.The polymerizable wetting agent can reduce the quiet of pressure sensitive adhesive
Electrical effect so that pressure sensitive adhesive is easy to paste after coated on base material, and it is more smooth to paste face, is not easy to adsorb dust, and adhere to
Power is strong, and this is that general acrylate pressure-sensitive adhesive hardly matches.
A kind of wall provided by the invention is with anti-disconnected acrylate pressure-sensitive adhesive mainly by soft monomer, hard monomer and function monomer
Copolymerization forms, and function monomer is acrylic acid PolyTHF ester and pyridine -2- acrylic acid, and acrylic acid PolyTHF ester has ether
The Long carbon chain of key, it is flexible relatively good, the tensile elongation of pressure sensitive adhesive can be significantly improved, pyridine -2- acrylic acid can be with wall
In Fe elements form coordination, enhancing and the bonding force of wall, therefore, the anti-disconnected acrylate pressure-sensitive adhesive of the wall has viscous
Close the advantages that intensity height, strong adsorption force, good weatherability, peel strength are high and elongation at break is high, can be very good applied to
The bonding of wall.
Beneficial effect：
1. the anti-disconnected acrylate pressure-sensitive adhesive of the wall of the present invention, has good weatherability properties and machinability.
2. the required raw material of the present invention is easy to get, simple production process, production cost is low, and accessory substance is few, efficiency high, is advantageous to
Industrialized production.
3. acrylic acid PolyTHF ester is incorporated into pressure sensitive adhesive by the present invention by way of copolymerization, the poly- tetrahydrochysene of acrylic acid
Furans ester has the Long carbon chain of ehter bond, flexible relatively good, can significantly improve the tensile elongation of pressure sensitive adhesive.
4. pyridine -2- acrylic acid is incorporated into pressure sensitive adhesive by the present invention by way of copolymerization, pyridine -2- acrylic monomers
In nitrogen can with wall base material ferro element formed be coordinated, so as to substantially increase the effect between adhesive and base material
Power, adhesive force greatly improve, and then obtain the wall pressure sensitive adhesive of high-adhesion energy.
5. the present invention is more preferable using the wetting agent wetting effect of polymerizable type so that the surface energy of wall base material reduces, from
And improve the interaction of adhesive and wall base material.
Embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
Bright rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, art technology
Personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Fixed scope.
The wall that a kind of number-average molecular weight of the present invention is 8000~300000 is used with anti-disconnected acrylate pressure-sensitive adhesive, wall
Anti- disconnected acrylate pressure-sensitive adhesive is mainly formed by the copolymerization of soft monomer, hard monomer and function monomer, and function monomer gathers for acrylic acid
Tetrahydrofuran ester and pyridine -2- acrylic acid, the molecular structural formula of acrylic acid PolyTHF ester are：
Wherein n=3~10；
Wall is to contain carbon carbon with polymerizable wetting agent, polymerizable wetting agent is also added into anti-disconnected acrylate pressure-sensitive adhesive
The mono-quaternaries cationic surfactant of double bond or the bis-quaternary ammonium salt cationic surfactant wall use containing carbon-carbon double bond
Anti- disconnected acrylate pressure-sensitive adhesive is not broken in the case of stretching 300%, and 180 ° of separation strengths are 2.0~4.0 pounds/25mm.
Embodiment 1
A kind of wall preparation method of anti-disconnected acrylate pressure-sensitive adhesive, is made up of the raw material below in terms of parts by weight：
Wherein the mass ratio of acrylic acid PolyTHF ester and pyridine -2- acrylic acid is 6:3；
The preparation of acrylic acid PolyTHF ester；
The PTMG that number-average molecular weight is 600 is dissolved in dichloromethane, PTMG
The concentration being dissolved in dichloromethane is 20wt%, is then added drop-wise in propylene isoxazolecarboxylic acid and reacts, PTMG with
The mol ratio of propylene isoxazolecarboxylic acid is 1:1, reaction temperature is 10 DEG C, reaction time 2h, is absorbed in course of reaction with triethylamine anti-
The mol ratio of caused hydrogen chloride gas during answering, triethylamine and propylene isoxazolecarboxylic acid is 1:1；Reaction product through extract and separate,
It is evaporated under reduced pressure and vacuum drying, generation acrylic acid PolyTHF ester, the molecular structural formula of acrylic acid PolyTHF ester is：
Wherein n=3；
Prepare wall is with the process conditions of anti-disconnected acrylate pressure-sensitive adhesive：
By above-mentioned raw materials formula by soft monomer ethyl acrylate, hard monomer acrylonitrile and acrylic acid PolyTHF ester and pyrrole
Pyridine -2- acrylic acid is dissolved in ethyl acetate, is well mixed, is then added to the 10% of mixture gross mass in reactor,
And initiator azodiisobutyronitrile is added dropwise, it is heated to 70 DEG C and starts to react, then drips remaining said mixture and initiator
It is added in reactor, was added dropwise to complete in 1 hour；Insulation 1 hour, room temperature is then cooled to, adds crosslinking agent toluene diisocyanate
Acid esters stirs, then discharging, obtains the anti-disconnected acrylate pressure-sensitive adhesive of the wall that number-average molecular weight is 8000.
Embodiment 2
A kind of wall preparation method of anti-disconnected acrylate pressure-sensitive adhesive, is made up of the raw material below in terms of parts by weight：
Wherein the mass ratio of acrylic acid PolyTHF ester and pyridine -2- acrylic acid is 7:3；
The preparation of acrylic acid PolyTHF ester；
The PTMG that number-average molecular weight is 2000 is dissolved in dichloromethane, PTMG
The concentration being dissolved in dichloromethane is 30wt%, is then added drop-wise in propylene isoxazolecarboxylic acid and reacts, PTMG with
The mol ratio of propylene isoxazolecarboxylic acid is 1.3:1, reaction temperature is 30 DEG C, reaction time 3h, is absorbed in course of reaction with triethylamine
The mol ratio of caused hydrogen chloride gas in course of reaction, triethylamine and propylene isoxazolecarboxylic acid is 1:1；Reaction product is through extraction point
From, be evaporated under reduced pressure and vacuum drying, generate acrylic acid PolyTHF ester, the molecular structural formula of acrylic acid PolyTHF ester
For：
Wherein n=10；
Prepare wall is with the process conditions of anti-disconnected acrylate pressure-sensitive adhesive：
By above-mentioned raw materials formula by soft monomer butyl acrylate, hard monomer acrylamide and the poly- tetrahydrochysene of function monomer acrylic acid
Furans ester and pyridine -2- acrylic acid are dissolved in ethyl acetate, are well mixed, are then added to the 15% of mixture gross mass
In reactor, and initiator azodiisobutyronitrile is added dropwise, is heated to 85 DEG C and starts to react, then by remaining said mixture and
Initiator azodiisobutyronitrile is added drop-wise in reactor, is added dropwise to complete in 4 hours；Insulation 2 hours, is then cooled to room temperature,
The toluene di-isocyanate(TDI) stirring of addition crosslinking agent, then discharging, obtain the anti-disconnected propylene of the wall that number-average molecular weight is 300000
Acid esters pressure sensitive adhesive.
Embodiment 3
A kind of wall preparation method of anti-disconnected acrylate pressure-sensitive adhesive, is made up of the raw material below in terms of parts by weight：
Wherein the mass ratio of acrylic acid PolyTHF ester and pyridine -2- acrylic acid is 6:3；
The preparation of acrylic acid PolyTHF ester；
The PTMG that number-average molecular weight is 1000 is dissolved in dichloromethane, PTMG
The concentration being dissolved in dichloromethane is 22wt%, is then added drop-wise in propylene isoxazolecarboxylic acid and reacts, PTMG with
The mol ratio of propylene isoxazolecarboxylic acid is 1.1:1, reaction temperature is 15 DEG C, reaction time 2.5h, is inhaled in course of reaction with triethylamine
The mol ratio of caused hydrogen chloride gas in receipts course of reaction, triethylamine and propylene isoxazolecarboxylic acid is 1:1；Reaction product is through extraction point
From, be evaporated under reduced pressure and vacuum drying, generate acrylic acid PolyTHF ester, the molecular structural formula of acrylic acid PolyTHF ester
For：
Wherein n=5；
Prepare wall is with the process conditions of anti-disconnected acrylate pressure-sensitive adhesive：
By above-mentioned raw materials formula by soft monomer acrylic acid-2-ethyl caproite, hard monomer styrene and function monomer acrylic acid
PolyTHF ester and pyridine -2- acrylic acid are dissolved in ethyl acetate, are well mixed, then by the 1% of mixture gross mass
It is added in reactor, and initiator azodiisobutyronitrile is added dropwise, is heated to 77 DEG C and starts to react, then will be remaining above-mentioned mixed
Compound and initiator are added drop-wise in reactor, are added dropwise to complete in 3 hours；Insulation 1.5 hours, is then cooled to room temperature, adds
Crosslinking agent 1, hexamethylene-diisocyanate stirring, then discharging, obtain the anti-disconnected acrylic acid of the wall that number-average molecular weight is 100000
Ester pressure-sensitive.
Embodiment 4
A kind of wall preparation method of anti-disconnected acrylate pressure-sensitive adhesive, is made up of the raw material below in terms of parts by weight：
Wherein the mass ratio of acrylic acid PolyTHF ester and pyridine -2- acrylic acid is 7:3；
The preparation of acrylic acid PolyTHF ester；
The PTMG that number-average molecular weight is 800 is dissolved in dichloromethane, PTMG
The concentration being dissolved in dichloromethane is 30wt%, is then added drop-wise in propylene isoxazolecarboxylic acid and reacts, PTMG with
The mol ratio of propylene isoxazolecarboxylic acid is 1.3:1, reaction temperature is 10 DEG C, reaction time 2.5h, is inhaled in course of reaction with triethylamine
The mol ratio of caused hydrogen chloride gas in receipts course of reaction, triethylamine and propylene isoxazolecarboxylic acid is 1:1；Reaction product is through extraction point
From, be evaporated under reduced pressure and vacuum drying, generate acrylic acid PolyTHF ester, the molecular structural formula of acrylic acid PolyTHF ester
For：
Wherein n=6；
Prepare wall is with the process conditions of anti-disconnected acrylate pressure-sensitive adhesive：
By above-mentioned raw materials formula by soft monomer EHMA, hard monomer methyl methacrylate and function monomer
Acrylic acid PolyTHF ester and pyridine -2- acrylic acid are dissolved in ethyl acetate, are well mixed, then by mixture gross mass
12% be added in reactor, and initiator benzoyl peroxide is added dropwise, is heated to 75 DEG C and starts to react, then will be remaining
Said mixture and initiator are added drop-wise in reactor, are added dropwise to complete in 3 hours；Insulation 1 hour, is then cooled to room temperature,
The toluene di-isocyanate(TDI) stirring of addition crosslinking agent, then discharging, obtain the anti-disconnected propylene of the wall that number-average molecular weight is 150000
Acid esters pressure sensitive adhesive.
Embodiment 5
A kind of wall preparation method of anti-disconnected acrylate pressure-sensitive adhesive, is made up of the raw material below in terms of parts by weight：
Wherein the mass ratio of acrylic acid PolyTHF ester and pyridine -2- acrylic acid is 6.5:3；
The preparation of acrylic acid PolyTHF ester；
The PTMG that number-average molecular weight is 1500 is dissolved in dichloromethane, PTMG
The concentration being dissolved in dichloromethane is 28wt%, is then added drop-wise in propylene isoxazolecarboxylic acid and reacts, PTMG with
The mol ratio of propylene isoxazolecarboxylic acid is 1.1:1, reaction temperature is 10 DEG C, reaction time 2h, is absorbed in course of reaction with triethylamine
The mol ratio of caused hydrogen chloride gas in course of reaction, triethylamine and propylene isoxazolecarboxylic acid is 1:1；Reaction product is through extraction point
From, be evaporated under reduced pressure and vacuum drying, generate acrylic acid PolyTHF ester, the molecular structural formula of acrylic acid PolyTHF ester
For：
Wherein n=9；
Prepare wall is with the process conditions of anti-disconnected acrylate pressure-sensitive adhesive：
By above-mentioned raw materials formula by soft monomer lauryl methacrylate, hard monomer methyl acrylate and function monomer
Acrylic acid PolyTHF ester and pyridine -2- acrylic acid are dissolved in ethyl acetate, are well mixed, then by mixture gross mass
15% be added in reactor, and initiator azodiisobutyronitrile is added dropwise, is heated to 80 DEG C and starts to react, then will be remaining
Said mixture and initiator azodiisobutyronitrile are added drop-wise in reactor, are added dropwise to complete in 1 hour；Insulation 1 hour, then
Room temperature is cooled to, adds the stirring of crosslinking agent methyl diphenylene diisocyanate, then discharging, it is 8000 to obtain number-average molecular weight
The anti-disconnected acrylate pressure-sensitive adhesive of wall.
Embodiment 6
A kind of wall preparation method of anti-disconnected acrylate pressure-sensitive adhesive, is made up of the raw material below in terms of parts by weight：
Wherein the mass ratio of ethyl acrylate and butyl acrylate is 1:1, acrylic acid PolyTHF ester and pyridine -2- third
The mass ratio of olefin(e) acid is 6:3；
The preparation of acrylic acid PolyTHF ester；
The PTMG that number-average molecular weight is 800 is dissolved in dichloromethane, PTMG
The concentration being dissolved in dichloromethane is 30wt%, is then added drop-wise in propylene isoxazolecarboxylic acid and reacts, PTMG with
The mol ratio of propylene isoxazolecarboxylic acid is 1:1, reaction temperature is 18 DEG C, reaction time 2h, is absorbed in course of reaction with triethylamine anti-
The mol ratio of caused hydrogen chloride gas during answering, triethylamine and propylene isoxazolecarboxylic acid is 1:1；Reaction product through extract and separate,
It is evaporated under reduced pressure and vacuum drying, generation acrylic acid PolyTHF ester, the molecular structural formula of acrylic acid PolyTHF ester is：
Wherein n=5；
Prepare wall is with the process conditions of anti-disconnected acrylate pressure-sensitive adhesive：
By above-mentioned raw materials formula by soft monomer ethyl acrylate and butyl acrylate, hard monomer acrylonitrile and function monomer third
Olefin(e) acid PolyTHF ester and pyridine -2- acrylic acid are dissolved in ethyl acetate, are well mixed, then by mixture gross mass
10% is added in reactor, and initiator azodiisobutyronitrile is added dropwise, and is heated to 75 DEG C and starts to react, then will be remaining on
State mixture and initiator azodiisobutyronitrile is added drop-wise in reactor, be added dropwise to complete in 2 hours；Insulation 1.5 hours, then
Room temperature is cooled to, adds the stirring of crosslinking agent azodiisobutyronitrile, then discharging, the wall that number-average molecular weight is 250000 is obtained and uses
Anti- disconnected acrylate pressure-sensitive adhesive.
Embodiment 7
A kind of wall preparation method of anti-disconnected acrylate pressure-sensitive adhesive, is made up of the raw material below in terms of parts by weight：
Wherein acrylic acid-2-ethyl caproite, and the mass ratio of EHMA is 2:1, acrylonitrile and acryloyl
The mass ratio of amine is 1:2, the mass ratio of acrylic acid PolyTHF ester and pyridine -2- acrylic acid is 7:3；
The preparation of acrylic acid PolyTHF ester；
The PTMG that number-average molecular weight is 600 is dissolved in dichloromethane, PTMG
The concentration being dissolved in dichloromethane is 26wt%, is then added drop-wise in propylene isoxazolecarboxylic acid and reacts, PTMG with
The mol ratio of propylene isoxazolecarboxylic acid is 1:1, reaction temperature is 15 DEG C, reaction time 2.5h, is absorbed in course of reaction with triethylamine
The mol ratio of caused hydrogen chloride gas in course of reaction, triethylamine and propylene isoxazolecarboxylic acid is 1:1；Reaction product is through extraction point
From, be evaporated under reduced pressure and vacuum drying, generate acrylic acid PolyTHF ester, the molecular structural formula of acrylic acid PolyTHF ester
For：
Wherein n=10；
Prepare wall is with the process conditions of anti-disconnected acrylate pressure-sensitive adhesive：
By above-mentioned raw materials formula by soft monomer acrylic acid-2-ethyl caproite and EHMA, hard monomer propylene
Nitrile and acrylamide and function monomer acrylic acid PolyTHF ester and pyridine -2- acrylic acid are dissolved in ethyl acetate, mixing
Uniformly, then the 18% of mixture gross mass is added in reactor, and initiator BP is added dropwise, be heated to 85 DEG C
Start to react, then remaining said mixture and initiator BP are added drop-wise in reactor, be added dropwise in 3 hours
Complete；Insulation 1 hour, room temperature is then cooled to, adds the stirring of crosslinking agent toluene di-isocyanate(TDI), then discharging, it is equal to obtain number
The anti-disconnected acrylate pressure-sensitive adhesive of the wall that molecular weight is 280000.
Embodiment 8
A kind of wall preparation method of anti-disconnected acrylate pressure-sensitive adhesive, is made up of the raw material below in terms of parts by weight：
Wherein the mass ratio of ethyl acrylate and butyl acrylate and acrylic acid-2-ethyl caproite is 1:1:2, acryloyl
Amine, the mass ratio of styrene are 1:2, the mass ratio of acrylic acid PolyTHF ester and pyridine -2- acrylic acid is 6:3；
The preparation of acrylic acid PolyTHF ester；
The PTMG that number-average molecular weight is 700 is dissolved in dichloromethane, PTMG
The concentration being dissolved in dichloromethane is 20wt%, is then added drop-wise in propylene isoxazolecarboxylic acid and reacts, PTMG with
The mol ratio of propylene isoxazolecarboxylic acid is 1:1, reaction temperature is 30 DEG C, reaction time 3h, is absorbed in course of reaction with triethylamine anti-
The mol ratio of caused hydrogen chloride gas during answering, triethylamine and propylene isoxazolecarboxylic acid is 1:1；Reaction product through extract and separate,
It is evaporated under reduced pressure and vacuum drying, generation acrylic acid PolyTHF ester, the molecular structural formula of acrylic acid PolyTHF ester is：
Wherein n=8；
Prepare wall is with the process conditions of anti-disconnected acrylate pressure-sensitive adhesive：
By above-mentioned raw materials formula by soft monomer ethyl acrylate and butyl acrylate and acrylic acid-2-ethyl caproite, hard single
Body acrylamide and styrene and function monomer acrylic acid PolyTHF ester and pyridine -2- acrylic acid are dissolved in ethyl acetate
In, it is well mixed, is then added to the 18% of mixture gross mass in reactor, and initiator benzoyl peroxide is added dropwise,
It is heated to 78 DEG C to start to react, then remaining said mixture and initiator benzoyl peroxide is added drop-wise in reactor,
It was added dropwise to complete in 4 hours；Insulation 1 hour, room temperature is then cooled to, adds crosslinking agent methyl diphenylene diisocyanate and stir
Mix, then discharging, obtain the anti-disconnected acrylate pressure-sensitive adhesive of the wall that number-average molecular weight is 260000.
Embodiment 9
A kind of wall preparation method of anti-disconnected acrylate pressure-sensitive adhesive, is made up of the raw material below in terms of parts by weight：
Wherein the mass ratio of styrene, methyl methacrylate and methyl acrylate is 2:1:1, acrylic acid PolyTHF
The mass ratio of ester and pyridine -2- acrylic acid is 7:3；
The preparation of acrylic acid PolyTHF ester；
The PTMG that number-average molecular weight is 1600 is dissolved in dichloromethane, PTMG
The concentration being dissolved in dichloromethane is 28wt%, is then added drop-wise in propylene isoxazolecarboxylic acid and reacts, PTMG with
The mol ratio of propylene isoxazolecarboxylic acid is 1.3:1, reaction temperature is 15 DEG C, reaction time 2.6h, is inhaled in course of reaction with triethylamine
The mol ratio of caused hydrogen chloride gas in receipts course of reaction, triethylamine and propylene isoxazolecarboxylic acid is 1:1；Reaction product is through extraction point
From, be evaporated under reduced pressure and vacuum drying, generate acrylic acid PolyTHF ester, the molecular structural formula of acrylic acid PolyTHF ester
For：
Wherein n=3；
Prepare wall is with the process conditions of anti-disconnected acrylate pressure-sensitive adhesive：
By above-mentioned raw materials formula by soft monomer lauryl methacrylate, hard monomer styrene, methyl methacrylate
Ester and methyl acrylate and function monomer acrylic acid PolyTHF ester and pyridine -2- acrylic acid are dissolved in ethyl acetate, are mixed
Close uniformly, be then added to the 16% of mixture gross mass in reactor, and initiator azodiisobutyronitrile is added dropwise, be heated to
75 DEG C start to react, and then remaining said mixture and initiator azodiisobutyronitrile are added drop-wise in reactor, small 2.5
When interior be added dropwise to complete；Insulation 1.5 hours, room temperature is then cooled to, adds the stirring of crosslinking agent toluene di-isocyanate(TDI), then go out
Material, obtain the anti-disconnected acrylate pressure-sensitive adhesive of the wall that number-average molecular weight is 15000.
Embodiment 10
A kind of wall preparation method of anti-disconnected acrylate pressure-sensitive adhesive, is made up of the raw material below in terms of parts by weight：
Wherein the mass ratio of EHMA and lauryl methacrylate is 1:2, acrylonitrile, acryloyl
The mass ratio 1 of amine and styrene:2:1, the mass ratio of acrylic acid PolyTHF ester and pyridine -2- acrylic acid is 6:3；
The preparation of acrylic acid PolyTHF ester；
The PTMG that number-average molecular weight is 1200 is dissolved in dichloromethane, PTMG
The concentration being dissolved in dichloromethane is 26wt%, is then added drop-wise in propylene isoxazolecarboxylic acid and reacts, PTMG with
The mol ratio of propylene isoxazolecarboxylic acid is 1.3:1, reaction temperature is 20 DEG C, reaction time 2h, is absorbed in course of reaction with triethylamine
The mol ratio of caused hydrogen chloride gas in course of reaction, triethylamine and propylene isoxazolecarboxylic acid is 1:1；Reaction product is through extraction point
From, be evaporated under reduced pressure and vacuum drying, generate acrylic acid PolyTHF ester, the molecular structural formula of acrylic acid PolyTHF ester
For：
Wherein n=7；
Prepare wall is with the process conditions of anti-disconnected acrylate pressure-sensitive adhesive：
By above-mentioned raw materials formula by soft monomer EHMA and lauryl methacrylate, hard monomer third
Alkene nitrile, acrylamide and styrene and function monomer acrylic acid PolyTHF ester and pyridine -2- acrylic acid are dissolved in acetic acid second
In ester, it is well mixed, is then added to the 15% of mixture gross mass in reactor, and initiator benzoyl peroxide first is added dropwise
Acyl, it is heated to 70 DEG C and starts to react, remaining said mixture and initiator benzoyl peroxide are then added drop-wise to reactor
In, it was added dropwise to complete in 3 hours；Insulation 2 hours, room temperature being then cooled to, add crosslinking agent 1, hexamethylene-diisocyanate stirs,
Then discharging, obtain the anti-disconnected acrylate pressure-sensitive adhesive of the wall that number-average molecular weight is 80000.
Claims (7)
1. a kind of anti-disconnected acrylate pressure-sensitive adhesive of wall, it is characterized in that：The wall is main with anti-disconnected acrylate pressure-sensitive adhesive
To be formed by the copolymerization of soft monomer, hard monomer and function monomer, described function monomer be acrylic acid PolyTHF ester and pyridine-
2- acrylic acid, the molecular structural formula of acrylic acid PolyTHF ester are：
Wherein n=3~10；
The wall with anti-disconnected acrylate pressure-sensitive adhesive in the case of stretching 300% it is not broken, 180 ° of separation strengths are 2.0~
4.0 pounds/25mm；
It is made up of the raw material below in terms of parts by weight：
The soft monomer, it is ethyl acrylate, butyl acrylate, acrylic acid-2-ethyl caproite, EHMA, first
One kind or wherein several combinations in base dodecylacrylate；
The hard monomer, be acrylonitrile, acrylamide, styrene, methyl methacrylate, one kind in methyl acrylate or its
In several combination；
The function monomer, is acrylic acid PolyTHF ester and pyridine -2- acrylic acid, wherein acrylic acid PolyTHF ester and
The mass ratio of pyridine -2- acrylic acid is 6~7:3.
2. the anti-disconnected acrylate pressure-sensitive adhesive of a kind of wall according to claim 1, it is characterised in that described wall is used
The number-average molecular weight of anti-disconnected acrylate pressure-sensitive adhesive is 8000~300000.
3. the anti-disconnected acrylate pressure-sensitive adhesive of a kind of wall according to claim 1, it is characterised in that described wall is used
Polymerizable wetting agent is also added into anti-disconnected acrylate pressure-sensitive adhesive, described polymerizable wetting agent is the list containing carbon-carbon double bond
Quaternary cationics or the bis-quaternary ammonium salt cationic surfactant containing carbon-carbon double bond.
4. a kind of wall as claimed in claim 1 preparation method of anti-disconnected acrylate pressure-sensitive adhesive, it is characterized in that：Acrylic acid
The preparation of PolyTHF ester；PTMG is dissolved in dichloromethane, is then added drop-wise in propylene isoxazolecarboxylic acid
Reaction, generate acrylic acid PolyTHF ester；
Prepare wall is with the process conditions of anti-disconnected acrylate pressure-sensitive adhesive：
Soft monomer, hard monomer and function monomer are dissolved in ethyl acetate by above-mentioned raw materials formula, are well mixed, then will be mixed
The 10~20% of compound gross mass are added in reactor, and described initiator is added dropwise, and are heated to 70~85 DEG C and are started to react,
Then remaining said mixture and initiator are added drop-wise in reactor, were added dropwise to complete in 1~4 hour；Insulation 1~2 is small
When, room temperature is then cooled to, adds crosslinking agent stirring, then discharging, obtains the anti-disconnected acrylate pressure-sensitive adhesive of described wall,
The number-average molecular weight of PTMG is 600~2000；PTMG is dissolved in dense in dichloromethane
Spend for 20~30wt%；The mol ratio of PTMG and propylene isoxazolecarboxylic acid is 1~1.3:1；Reaction temperature be 10~
30 DEG C, 2~3h of reaction time；With triethylamine come caused hydrogen chloride gas, triethylamine during absorbing reaction in course of reaction
Mol ratio with propylene isoxazolecarboxylic acid is 1:1；Reaction product is through extract and separate, vacuum distillation and vacuum drying.
A kind of 5. wall according to claim 4 preparation method of anti-disconnected acrylate pressure-sensitive adhesive, it is characterised in that institute
The initiator stated is azodiisobutyronitrile or benzoyl peroxide.
A kind of 6. wall according to claim 4 preparation method of anti-disconnected acrylate pressure-sensitive adhesive, it is characterised in that institute
The crosslinking agent stated is polyisocyanates, and specially oneself is two different by toluene di-isocyanate(TDI), methyl diphenylene diisocyanate or 1,6-
Cyanate.
7. a kind of wall according to claim 4 preparation method of anti-disconnected acrylate pressure-sensitive adhesive, it is characterised in that former
The polymerizable wetting agent that parts by weight are 1~3 is also added into material, described polymerizable wetting agent is the list containing carbon-carbon double bond
Quaternary cationics or the bis-quaternary ammonium salt cationic surfactant containing carbon-carbon double bond.
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| GB2562747B (en) | 2017-05-23 | 2019-06-26 | Henkel IP & Holding GmbH | Low-viscosity photocurable adhesive compositions |
| CN114853939A (en) * | 2022-05-11 | 2022-08-05 | 苏州德佑新材料科技股份有限公司 | Solvent type acrylate pressure-sensitive adhesive and preparation method thereof |
| CN115745844B (en) * | 2022-11-30 | 2024-04-16 | 厦门琪星新材料有限公司 | Photoinitiator, adhesive using same and preparation methods of photoinitiator and adhesive |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101798491A (en) * | 2010-02-25 | 2010-08-11 | 北京高盟新材料股份有限公司 | Pressure sensitive adhesive for protective film and preparation method thereof |
| CN103554340A (en) * | 2013-10-27 | 2014-02-05 | 合肥乐凯科技产业有限公司 | Acrylate emulsion for improving adhesive force of polyester film and preparation method thereof |
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| CN102850972B (en) * | 2012-08-30 | 2014-01-15 | 烟台德邦科技有限公司 | Pressure-sensitive adhesive and preparation method thereof |
| CN103031089B (en) * | 2012-11-26 | 2015-04-22 | 浙江大学宁波理工学院 | Polyacrylate adhesive for calcium plastic corrugated paper and preparation method thereof |
| CN103305163A (en) * | 2013-06-17 | 2013-09-18 | 昆山韩保胶带科技有限公司 | Novel high-performance pressure-sensitive adhesive for double-sided adhesive tape and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798491A (en) * | 2010-02-25 | 2010-08-11 | 北京高盟新材料股份有限公司 | Pressure sensitive adhesive for protective film and preparation method thereof |
| CN103554340A (en) * | 2013-10-27 | 2014-02-05 | 合肥乐凯科技产业有限公司 | Acrylate emulsion for improving adhesive force of polyester film and preparation method thereof |
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| Title |
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| 长链醇丙烯酸酯合成方法的研究进展;毛文娟，许孝良;《浙江化工》;20141231;第45卷(第9期);正文第3段 * |
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