CN101089031A - Polysiloxane with (methyl) propenoic acid ester base and its use - Google Patents
Polysiloxane with (methyl) propenoic acid ester base and its use Download PDFInfo
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- CN101089031A CN101089031A CN 200610083961 CN200610083961A CN101089031A CN 101089031 A CN101089031 A CN 101089031A CN 200610083961 CN200610083961 CN 200610083961 CN 200610083961 A CN200610083961 A CN 200610083961A CN 101089031 A CN101089031 A CN 101089031A
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Abstract
The present invention discloses polysiloxane with (methyl) acrylate radical and monocarboxlic ester radical and its use in radiation cured abhesion paint. The modified polysiloxane may be well adhered to the coated carrier in high curing rate, and the cured coating has high chemical and physical stability and high flexibility. The present invention has properly matched abhesion performance and adhesive characteristic to reach required abhesion degree.
Description
Technical field
Present invention relates in general to new, have (methyl) the acrylate-based polysiloxane that connects by the SiC base.
Consider from another point of view, the invention still further relates to and comprise above-mentioned new unsticking (abhesive) coating and composition polysiloxane, that be used for the radiation-hardenable of chip carrier (sheet-like support), and the coated product with described polysiloxane coating of radiation curing.
Background technology
Unsticking coating is used to apply flaky material on a large scale, to reduce the adhesion tendency of viscous product to the surface.The unsticking coating composition is used for, and for example, applies paper or film as the Pressuresensitive Label carrier.Label with pressure sensitive adhesive is bonded on the surface of band coating, and its bondability only is enough to make and can operates adhesive label's carrier film.Yet, must label be left behind from the carrier film of band coating, can not cause the significantly sacrificing of bounding force to use simultaneously again to treat the back.Other of unsticking coating composition used also has wrapping paper, especially for the wrapping paper of packing adhesive article.This unsticking paper or unsticking film are used for, for example, and wrap food or Industrial products, for example packaged asphalt.
Make the unsticking coating composition, crosslinkable organopolysiloxane, particularly acrylate group modified radiation-hardenable organopolysiloxane, verified they self value.
For example, German Patent 2, disclose in 948,708 and a kind ofly prepared the method for the organopolysiloxane of pentaerythritol triacrylate or pentaerythritol acrylate trimethyl modification by organochlorine for polysiloxane, wherein optional (HCl-binding) neutralizing agent that adds the HCl associativity; In this method, the general formula of organopolysiloxane is following:
(R
1Alkyl, vinyl and/or the phenyl of=1 to 4 carbon atom, prerequisite are the R of at least 90 molar percentages
1Base is a methyl; " a " is numerical value 1.8 to 2.2; " b " is numerical value 0.004 to 0.5), this organopolysiloxane at first reacts based on the dialkylamine of SiCl base with at least 2 molar weights, the alkyl of described dialkylamine respectively has 3 to 5 carbon atoms, and the carbon atom that closes on nitrogen carries separately and is no more than a hydrogen atom.This reaction product and the pentaerythritol triacrylate or the pentaerythritol acrylate trimethyl of equimolar amount are at least reacted, by currently known methods solids component is separated with final product then.
Coating composition by this method preparation has shown good unsticking, has kept its bounding force to the substrate of being untreated largely with the contacted sealing tape of coating composition.Yet, fixedly be this unsticking performance should be all the time combined in conjunction with the chemical structure of tackiness agent and structure treat, and coating to be to show the unsticking performance at tackiness agent.Therefore, with regard to German Patent 2,948, disclosed unsticking coating in 708 is because its performance can't allocate different tackiness agents, so this unsticking coating can't all can provide gratifying effect in all cases.
Show improved performance by (methyl) acrylate modified organopolysiloxane mixture, described mixture is characterised in that they are composed of the following components: reaching equilibrated on average has＞and the organopolysiloxane of 25 to＜200 Siliciumatoms, the organopolysiloxane that 2 to 25 Siliciumatoms are on average arranged of 2 to 30 weight %, and the organopolysiloxane that 200 to 2,000 Siliciumatoms are on average arranged of 2 to 30 weight %.The various organopolysiloxanes that contained in the above-mentioned tertiary mixture are born different tasks.The task of low molecular weight part mainly is that coating composition is bonded in the substrate.The effect of high molecular part mainly is to make coating composition have required unsticking performance.Middle portion is a curable matrix, particularly determines the physicals of coating composition.What those of ordinary skills will understand is, more than only be the concise and to the point description of the performance and the task of three kinds of different pieces because unsticking apply agent the complicated performance that must have have only combined action to realize by three kinds of compositions.Adopt the modification organopolysiloxane mixture of German Patent 3,426,087, improved the unsticking performance of mixture on the one hand, improved also that on the other hand coating is coated with the also adhesive performance of solidified substrate thereon viscous surface.However, the performance of determining these coating compounds still can't suitably be allocated at different tackiness agents.
European patent application discloses text (Offenlegungsschrift) but has narrated a kind of electrocuring liquid coating in 0159683.Described coating should comprise following component:
1.60 to 95 parts organopolysiloxane, described polysiloxane per molecule contains and surpasses about 25 siloxanes, and per molecule contain 2 to 10 parts reaction methanol-based (carbonyl), other substituting group of silicon is the alkyl of 1 to 20 carbon atom; The methanol-based (carbinol) of having reacted is defined as the ester of vinylformic acid, methacrylic acid or mixture, or the ether of the hydroxy alkyl ester of described acid, and described alkyl comprises 2 to 4 carbon atoms; The unreacted methanol base should no longer exist basically, so that hydroxyl value is less than 10;
2.3, contain 2 to 4 hydroxyls in the described polyvalent alcohol per molecule, and the molecular weight of described polyvalent alcohol is less than 1,200 to the polyester of 25 parts polyvalent alcohols and vinylformic acid, methacrylic acid or these sour mixtures;
3.1 to 10 parts by weight of acrylic, methacrylic acid or these sour mixtures.
The additional use of (methyl) acrylate of polyvalent alcohol has improved solidification rate; Yet on the other hand, the increase of organic moiety is but to the flexibility and the unsticking generation adverse influence of coating.Containing free acrylic or methacrylic acid composition is the another one defective.This one-tenth branch produces a kind of disgusting smell, also can make operation become difficult in the process of material coating to be coated.
With acrylate-based organopolysiloxane radiation-hardenable, a series of other application of this organopolysiloxane have therefore been reported.Acrylate modified organopolysiloxane is used as japanning, in order to sealing and embedding electrical element and electronic component, and in order to make moulded products.About the possible structure of described acrylate modified organopolysiloxane, the open text of following patent application, patent authorization text (Auslegeschrift) and patent are proposed:
German Patent authorization text 2,335,118 relates to the acrylate-based organopolysiloxane that contains of the following optional replacement of a kind of general formula,
(the monovalence alkyl of R=hydrogen or 1 to 12 carbon atom; R
1The monovalence alkyl or the cyano group alkyl of=optional halogenated 1 to 8 carbon atom; R " the bivalent hydrocarbon radical of=1 to 18 carbon atom or contain the bivalent hydrocarbon radical of C-O-C key; R =R ' O
0.5Or R
3' SiO
0.5Z=OR ', R ' or OSiR
3'; R '=1 is to the alkyl of 12 carbon atoms; " a " and " b " represents numeral 1 to 20,000 respectively; C is a numeral 0 to 3; E is a numeral 0 to 2; At least one Z base is OR ' when c=0).Described siloxane polymer can be used as the intermediate that preparation contains the pulsating multipolymer of organopolysiloxane, and this multipolymer can be used as coating composition.In addition, the siloxane polymer of this acrylate functional also can be used as the protective coating compositions of sizing material and paper and fabric.Yet these products are not suitable for preparing unsticking coating.In addition, Germany's authorization patent text 2,335, the ester modified polysiloxane of 118 linear diacrylate contains the group of alkoxyl group by its definition, this group can and cause polysiloxane further crosslinked by the hydrolysis removal, also can destroy its elasticity simultaneously, and elasticity is very important for coating composition.
The open text DE3 of German patent application discloses a kind of polysiloxane with pendant acrylate groups in 044,237, and epoxy-functional siloxanes that described polysiloxane can be by making ad hoc structure and vinylformic acid react and makes.The product radiation-hardenable that obtains.These products can be used as the low viscosity lacquer, are coated on the conventional oil base printing ink.Yet, a hydroxyl on the other side is all arranged owing to each is acrylate-based, bigger limitation is arranged when therefore above-mentioned product is as the unsticking coating composition.
United States Patent (USP) 4,568,566 disclose a kind of curable silicone goods composed of the following components:
A) molecular formula of 75 to 100 molar percentages is R
3SiO
0.5, RSiO
1.5And SiO
2(chemically bound) siloxy units of chemical bonding; With
B) R of 0 to 25 molar percentage
2The SiO unit, wherein a plurality of R unit has following structure
R wherein
1Be the alkyl of hydrogen or 1 to 12 carbon atom, R
2Be bivalent hydrocarbon radical or alkylidene oxide.Described curable product is used in particular for applying electronic component, also as fibre-optic coating.Yet, because the R of this class curable product
2SiO unit content is too low, so it is not suitable for the unsticking coating as chip carrier.
The purpose of the open text 0,152,179 of european patent application is a kind of silicone articles of curable elastomer-forming.These goods are composed of the following components: a) a kind of silicone resin of linear structure, described resin on average contains at least 150 siloxane units, and the terminal acrylic that connects, wherein the zone between the acrylic that connects does not endways have acrylic, b) light trigger at least 10% silicon-dioxide in small, broken bits, and c).This class material is as tackiness agent and sealed composite thing (sealing compound).
At last, with reference to the open text 0,169,592 of european patent application.The open text of this european patent application relates to a kind of optical glass fibre with synthetic coating, described optical glass fibre comprises glass fibre and elastomeric parcel coating, and wherein the specific refractory power of synthetic rubber parcel coating is greater than the outer field specific refractory power of glass fibre.Synthetic rubber is formed by the curable plastics composite that contains multipolymer, and described multipolymer comprises dimethyl siloxane and at least a siloxanes of methylphenyl siloxane and diphenyl siloxane that is selected from as monomeric unit.Comprise at least two acrylate groups in the described silicone copolymers per molecule, be characterised in that and also contain molecular-weight average in the curable synthetic composition greater than 3,000 urethane acrylate.The polysiloxane that proposes in its claim can have following structure:
A primary condition is that described polysiloxane has the phenyl that links to each other with silicon.This phenyl composition is to make the prerequisite of the specific refractory power of coating composition near the specific refractory power of fibre-optic glass.Yet combining with urethane acrylate from these siloxanes is used for applying the purposes of optical glass fibre, can not draw the conclusion that this compounds also can be used as the unsticking coating composition.
At periodical " polymer chemistry " (Makromolekulare Chemie), (RapidCommunication), 7, (1986) have reported the method for the linear methyl polysiloxane of anamorphic zone methacrylate end-groups in the 703rd to 707 page.In this synthetic method, α, addition reaction takes place in ω-hydrogen dimethylamino based polysiloxane and allyl group glycidyl ethers in the presence of Platinic chloride.The di-epoxide that generates in the presence of di-isopropyl Whitfield's ointment chromium with the methacrylic acid-respons, obtain required methacrylic ester.Described ester can two kinds of isomer form exist:
(alpha-isomer)
(β-isomer)
If (methyl) acrylate begins preparation by the method for prior art from the epoxy-functional siloxanes, then epoxy group(ing) is reacted with (methyl) vinylformic acid.By opening the epoxide ring, generate list (methyl) acrylate that contains a vicinal hydroxyl groups.
Summary of the invention
An object of the present invention is to provide the unsticking coating composition based on (methyl) acrylate modified organopolysiloxane, known coating composition is compared the performance with improvement in described composition and the industry.
More specifically, an object of the present invention is to provide a kind of coating composition that can allocate at the different product of bonding situation (tackiness agent).
The organopolysiloxane of described (methyl) acrylate-based modification must have the particularly combination of following performance:
1. to the gratifying clinging power of specific carrier to be coated
2. the high solidification rate on carrier
3. the chemistry and the physical stability of the coating after solidifying
4. the high flexibility of the coating after solidifying
5. to the unsticking performance of viscous product, but and unsticking coating to the adaptation ability of adhesive chemistry characteristic
6. the adjustable characteristic of required unsticking degree.
(methyl) the acrylate-based polysiloxane that has by the connection of SiC key that is combined as of above-mentioned performance has, and described polysiloxane obtains by following (A) and reaction (B),
(A) the following polysiloxane of general formula
In this formula
R
1Base is identical or different, and represents the low alkyl group of 1 to 4 carbon atom separately
Or phenyl,
R
2Base can a part be R
1If a part of R
2=R
1, then remaining R
2The base representative
Epoxy-functional group up to 70 to 100%, and
The alkyl or the hydrogen of 2 to 10 carbon atoms up to 30 to 0%,
Prerequisite is to comprise at least 1.8 epoxy group(ing) in the average molecule;
A is a numerical value 1 to 1,000, and
B is a numerical value 0 to 10,
(B) based on epoxide group, (methyl) vinylformic acid of 0.4 to 0.9 molar weight, and remaining epoxide group with do not react with a kind of monocarboxylic acid of polymerizable double bond.
General formula I is the average structure formula of the required epoxy-functional organopolysiloxane of reaction.Independent structure block (building block) (on the statistical significance) randomly is distributed in the mixture of polymers.
Functional unit [R
1, R
2SiO-] summation be a (2+b).Trifunctional units [R
1SiO
3/2-] number provide by subscript " b "." a " is numerical value 1 to 1,000, preferred value 5 to 200." b " is numerical value 0 to 10, preferred 0 to 2.If b=0, then this epoxy-functional organopolysiloxane has the chain linear structure.By subscript " a " and " b " though the epoxy-functional organopolysiloxane of definition with (methyl) vinylformic acid and the reaction of other monocarboxylic acid after still keep its structure.
In polymerizable molecular, R
1Can be identical or different, and represent a low alkyl group or the phenyl that 1 to 4 carbon atom is arranged.Described alkyl can be straight chain or have side chain.Preferably, at least 90% R
1Base is a methyl.
R
2Base can a part be represented R
1Base.Remaining R
2In the base, up to 70 to 100% be the epoxy-functional group.Be interpreted as and each group that have epoxy group(ing) that link to each other at this epoxy-functional group with siloxane backbone (framework) by the SiC key.Epoxy-functional R
2The preferred embodiment of base is
In the epoxy-functional polysiloxane of formula I, preparation process can produce has the R that implication is a hydrogen
2Base.
R up to 30%
2Base can be the alkyl or the hydrogen of 2 to 20 carbon atoms.Described alkyl can be chosen wantonly by halogen or phenyl and replace.Be fit to and preferred R
2The example of alkyl is ethyl, propyl group, normal-butyl, isobutyl-, hexyl, octyl group, dodecyl, octadecyl, 2-phenyl propyl and 3-chloropropyl.
Be R
2When base is selected different implication, should follow following condition, at least 1.8 R in the promptly average molecule
2Base is the epoxy-functional group.Numerical value 1.8 is interpreted as a mathematical mean of polyblend.
Organopolysiloxane of the present invention can obtain by following reaction: the epoxy-functional organopolysiloxane that makes general formula I earlier with (methyl) vinylformic acid, again with not with the monocarboxylic acid of polymerizable double bond so that all esterified amount of all epoxide groups react.What in this respect, (methyl) vinylformic acid was intended to represent to use is the mixture of acrylic or methacrylic acid or described two kinds of acid.At this on the one hand, following prerequisite is most important to the present invention, promptly based on epoxide group, had (methyl) vinylformic acid of 0.4 to 0.9 molar weight and the different with it monocarboxylic acid of following amount to participate in reaction, described monocarboxylic amount is enough to finish the reaction of epoxide group.This just requires such prerequisite: based on epoxide group, use the acid of equimolar amount at least.Advantageously, after reaction, remove any excessive not polymerisable monocarboxylic acid.
Alkyl carboxylic acid and phenylformic acid are considered to not be with the monocarboxylic acid of polymerizable double bond.With regard to alkyl carboxylic acid, the alkyl carboxylic acid of preferred 2 to 11 carbon atoms.Monocarboxylic example is acetate, propionic acid, butyric acid, valeric acid, PIVALIC ACID CRUDE (25), 2,2-acid dimethyl, 2,2-dimethyl valeric acid, etheric acid, octane-iso carboxylic acid, isodecane carboxylic acid, Sorbic Acid and undecanoic acid.
Especially preferred monocarboxylic acid is an acetate.
In organopolysiloxane of the present invention, the epoxy-functional R of 40 to 90 molar percentages
2Base exists with the form of its (methyl) acrylate.Remaining epoxy-functional R
2Base exists with the form with the monocarboxylic ester of polymerizable double bond not.
The adjusting that the performance of organopolysiloxane of the present invention is carried out is within the limit of power of those of ordinary skills (expert) in the following manner:
1. after organopolysiloxane of the present invention solidified, its unsticking performance improved along with (methyl) increasing of acrylate-based number in the polymer molecule.Along with cross-linking density increases, the second-order transition temperature of the coating after the curing raises, and flexible the reduction.Simultaneously, the chemical stability of the coating after the curing and physical stability increase.
2. increase along with the ratio with the monocarboxylic acid ester group of polymerizable double bond not, this unsticking performance reduces, and the clinging power of carrier is strengthened.By selecting monocarboxylic acid, unsticking coating is allocated at the chemical property of tackiness agent.
3. because up to 30% R
2Base can be the alkyl of optional 2 to 20 carbon atoms that replace, and therefore has the another kind of possibility that influences the unsticking performance.Because of the event of the alkyl that has 2 to 20 carbon atoms, the organic trait of modified polyorganosiloxane improves.From this on the one hand, it is generally acknowledged content that can be by improving alkyl and increase the chain length of alkyl and reduce the unsticking performance of polysiloxane selectively.
Therefore organopolysiloxane of the present invention is particularly suited for regulating or allocating at specific technology application.Therefore described organopolysiloxane is particularly suited for the unsticking coating composition as radiation-hardenable.
Below provided the example of polysiloxane with and monocarboxylic acid ester group acrylate-based by (methyl) of the connection of SiC base.Only non-limited way provides these examples in the explanation mode.
Compound 1
Wherein
Compound 2
R wherein
1=H, CH
3
Compound 3
R wherein
1=H, CH
3
Compound 4
A
5As the definition in the compound 3,
R wherein
1=H, CH
3
Compound 5
Wherein
R
1＝H，CH
3
m＝0.9
n＝0.1。
Compound 6
A
3As the definition in the compound 2,
A
10＝-(CH
2)
5-CH
3。
Compound 7
A
1As the definition in the compound 1
A
11＝-(CH
2)
7-CH
3，
Wherein
R
1＝H，CH
3
m＝0.59
n＝0.37
o＝0.04。
Compound 8
A
3, A
4As the definition in the compound 2.
Compound 9
A
3, A
4As the definition in the compound 2.
Compound 10
A
3, A
4As the definition in the compound 2.
Organopolysiloxane of the present invention is by the preparation of the known way in the industry.For example, the epoxy-functional organopolysiloxane for preparation formula I can use wherein R
1Represent the hydrogen polysiloxanes of hydrogen.Described hydrogen polysiloxanes and R
2*Addition reaction, R take place in base
2*Base and R
2Base is corresponding, but has the two keys of an alkene on the end of plan and Si atomic bonding.In this reaction, may keep unreacted SiH base in the product, therefore, because reaction conditions is, polysiloxane of the present invention can comprise a spot of hydrogen as R
2Group.
The epoxide group of the epoxy-functional polysiloxane of formula I reacts by (methyl) vinylformic acid of following reaction and 0.4 to 0.9 mole---every epoxide group---.
R＝H，CH
3。
The epoxide group of remaining 0.1 to 0.6 molar part now in an identical manner with can not reacting by the polymeric monocarboxylic acid of equivalent (being excessive when needing) at least.
Reaction can especially be carried out under 80 to 150 ℃ at elevated temperatures, if desired, also can solvent for example toluene in the presence of carry out.
Can pass through conventional catalyst enhance esterification, for example alkaline-earth oxide, amine, acid or metal-salt.Select described catalyzer will make contingent open loop side reaction remain on low degree.Because esterification is undertaken by the general known rule of this reaction, so particular case can be with reference to organic synthesis handbook commonly used.
Randomly, for avoiding the generation of premature polymerization, can in esterification reaction process, add the known stopper of significant quantity, as quinhydrones.
Another object of the present invention is the purposes of polysiloxane of the present invention as the radiation-hardenable unsticking coating of chip carrier.Itself can directly use product of the present invention.Only under UV solidified situation, just must add radical initiator in modified polyorganosiloxane, its add-on is 2 to 5 weight % based on siloxanes.
The selection of radical initiator is based on the wavelength spectrum that solidifies the source of radiation that is adopted.Described radical initiator is known, and the example is benzophenone, diphenyl-ketoxime or benzoin ether.
Can carry out modification by adding other products to the coating composition that obtains thus in a known manner.Described known properties-correcting agent is the siloxanes with following group, and described group is incorporated into coating composition with chemical mode in solidification process.What especially be suitable as properties-correcting agent is the siloxanes with the hydrogen atom that links to each other with Siliciumatom.The producible variation of described properties-correcting agent is coated on the chip carrier thereby make it easier such as reducing the coating composition viscosity.
Also might add additive in coating, described additive is sealed by coating composition in solidification process as inert substance.The example that is scattered in the described material in the coating composition comprises the silicon-dioxide of high dispersing or the polymkeric substance of fluorinated hydrocarbons.
The preparation and the application performance of the polysiloxane of (methyl) of the present invention acrylate-based modification will be narrated in following example.What should understand is that non-limited way provides following in the explanation mode
Example.
Example 1 (the present invention)
Under 90 ℃, 248g (2mol) the vinyl cyclohexene oxide compound in 4 liters of three-necked flasks, 4mgH
2PtCl
66H
2O is dissolved in the solution (40mL) of 3mL glycol dimethyl ether and splashes into the following polydimethylsiloxane that contains the SiH base of 1170g (1mol) average structure formula.
100 ℃ after following 7 hours, with 500g toluene, 8g1,4-diazabicyclo (2,2,2) octane and 0.2g quinhydrones add in the following epoxy-functional polydimethylsiloxane of the average structure formula that obtains thus.
Splash into 130g (1.8mol) vinylformic acid subsequently, drop rate makes temperature be no more than 120 ℃.100 ℃ after following 10 hours, add 24g (0.4mol) acetate.Under 100 ℃ again after 20 hours, through distillation (100 ℃, 60torr) and obtain the moderately viscous reddish-brown oily matter of 1440g (theoretical yield 92%) after filtering.According to
1H NMR spectrum, this oily matter has following general formula
A
1, A
2As the definition in the compound 1,
m＝0.9
n＝0.1
R
1＝H。
Example 2 (non-the present invention)
As example 1, by 570g (5mol) allyl glycidyl ether and the following polydimethylsiloxane that contains the SiH base of 1794g (1mol) average structure formula,
(CH
3)-D
19-D
5′-Si-(CH
3)
3
The following epoxy-functional polydimethylsiloxane of preparation average structure formula.
What add 68gCordova Chemical in this product contains chromium (III) catalyst A MC2 and 0.3g quinhydrones.Splash into 360g (5mol) vinylformic acid subsequently, drop rate makes temperature be no more than 120 ℃.100 ℃ after following 30 hours, distillation (100 ℃ 60torr) and filter, obtain 2, the moderately viscous deep green oily matter of 615g (theoretical amount 96%).According to
1H NMR spectrum, this oily matter has following general formula
A wherein
3As the definition in the compound 2.
Example 3 (the present invention)
With the epoxy-functional polydimethylsiloxane with following average structure formula of example 2 preparation (2,364g 1mol) mixes with 68gAMC2 and 0.3g quinhydrones,
A wherein
14As the definition in the example 2.
(288g 4mol), adds speed and makes temperature be no more than 120 ℃ to add vinylformic acid.100 ℃ after following 10 hours, add 120g acetate.Under 100 ℃ again after 20 hours, distillation (100 ℃ 60torr) and filter, obtain 2, the moderately viscous deep green oily matter of 600g (theoretical amount 96%).According to
1H NMR spectrum, this oily matter has following general formula
A wherein
3And A
4As the definition in the compound 2.
Example 4 (the present invention)
As example 1, by 560g (8mol) 1,3-butadiene monoxide and 11, the following polydimethylsiloxane that contains the SiH base of 594g (1mol) average structure formula,
CH
3-D
149-D
8′-Si-(CH
3)
3
The following epoxy-functional polydimethylsiloxane of preparation average structure formula.
As example 3, this product and 403g (5.6mol) vinylformic acid and 446g (2.4mol) undecanoic acid are reacted.100 ℃ after following 30 hours, distillation (100 ℃ 60torr) and filter, obtain 12, the moderately viscous deep green oily matter of 350g (theoretical amount 95%).According to
1H NMR spectrum, this oily matter has following general formula,
A wherein
5And A
6As the definition in the compound 3.
Example 5 (the present invention)
As example 3, make example 4 preparation the epoxy-functional polydimethylsiloxane with following average structure formula (12,150g 1mol) reacts with 403g (5.6mol) vinylformic acid and 144g (2.4mol) acetate,
A wherein
15As the definition in the example 4.100 ℃ after following 30 hours, distillation (100 ℃ 60torr) and filter, obtain 12, the moderately viscous deep green oily matter of 060g (theoretical amount 95%).According to
1H NMR spectrum, this oily matter has following general formula
A wherein
5As the definition in the compound 3, and
A
7As the definition in the compound 4.
Example 6 (the present invention)
As example 1, by 608g (4mol) limonene monoxide and the following polydimethylsiloxane that contains the SiH base of 2474g (1mol) average structure formula,
The following epoxy-functional polydimethylsiloxane of preparation average structure formula.
Same as example 1, add 260g (3.6mol) vinylformic acid and 24g (0.4mol) acetate.100 ℃ after following 30 hours, distillation (100 ℃ 60torr) and filter, obtain 3, the moderately viscous reddish-brown oily matter of 164g (theoretical amount 94%).According to
1H NMR spectrum, this oily matter has following general formula
A
8And A
9As the definition in the compound 5.
m＝0.9
n＝0.1
R
1＝H。
Example 7 (the present invention)
As example 1, by 912g (8mol) allyl glycidyl ether, 252g (3mol) 1-hexene and 11, the following polydimethylsiloxane that contains the SiH base of 774g (1mol) average structure formula,
CH
3-D
149-D
11′-Si-(CH
3)
3
The following epoxy-functional polydimethylsiloxane of preparation average structure formula,
A wherein
14As the definition in the example 3, and
A
10As the definition in the compound 6.
As example 3, this product and 403g (5.6mol) vinylformic acid and 144g (2.4mol) acetate are reacted.100 ℃ after following 30 hours, distillation (100 ℃ 60torr) and filter, obtain 13, the moderately viscous deep green oily matter of 080g (theoretical amount 97%).According to
1H NMR spectrum, this oily matter has following general formula
A wherein
3And A
4As the definition in the compound 2,
And A
10As the definition in the compound 6.
Example 8 (the present invention)
As example 1, by 1,120g (10mol) octene, 868g (7mol) vinyl cyclohexene oxide compound and 20, the following polydimethylsiloxane that contains the SiH base of 286g (1mol) average structure formula,
The following epoxy-functional polydimethylsiloxane of preparation average structure formula,
A wherein
13As the definition in the example 1,
A
11As the definition in the compound 7,
m＝0.59，
n＝0.41。
As example 3, make the reaction of this product and 454g (6.3mol) vinylformic acid and 52g (0.7mol) propionic acid.100 ℃ after following 30 hours, distillation (100 ℃ 60torr) and filter, obtain 21, the moderately viscous deep green oily matter of 500g (theoretical amount 93%).According to
1H NMR spectrum, this oily matter has following general formula
A wherein
1As the definition in the compound 1,
A
11And A
12As the definition in the compound 7,
m＝0.59，
n＝0.37
o＝0.04。
Example 9 (non-the present invention)
As example 1, by 1,140g (10mol) allyl glycidyl ether and 2, the following polydimethylsiloxane that contains the SiH base of 760g (1mol) average structure formula,
CH
3-D
28-D
10′-Si-(CH
3)
3
The following epoxy-functional polydimethylsiloxane of preparation average structure formula,
A wherein
14As the definition in the example 2.
As example 2, make the reaction of this product and 720g (10mol) vinylformic acid.100 ℃ after following 30 hours, distillation (100 ℃ 60torr) and filter, obtain 4, the moderately viscous deep green oily matter of 430g (theoretical amount 96%).According to
1H NMR spectrum, this oily matter has following general formula
A wherein
3As the definition in the compound 2.
Example 10 (the present invention)
As example 3, the epoxy-functional polydimethylsiloxane that the average structure formula that example 9 is prepared is following (3,900g 1mol) reacts with 120g (2mol) acetate and 576g (8mol) vinylformic acid,
A wherein
14As the definition in the example 2.
100 ℃ after following 30 hours, distillation (100 ℃ 60torr) and filter, obtain 4, the moderately viscous deep green oily matter of 410g (theoretical amount 96%).According to
1H NMR spectrum, this oily matter has following general formula
A wherein
3And A
4As the definition in the compound 2.
Example 11 (the present invention)
As example 3, the epoxy-functional polydimethylsiloxane that the average structure formula that example 9 is prepared is following (3,900g 1mol) reacts with 432g (6mol) vinylformic acid and 240g (4mol) acetate,
A wherein
14As the definition in the example 2.
100 ℃ after following 30 hours, distillation (100 ℃ 60torr) and filter, obtain 4, the moderately viscous deep green oily matter of 390g (theoretical amount 96%).According to
1H NMR spectrum, this oily matter has following general formula
A wherein
3And A
4As the definition in the compound 2.
Example 12 (the present invention)
The epoxy-functional polydimethylsiloxane that the average structure formula of example 9 preparations is following (3,900g 1mol) reacts with 288g (4mol) vinylformic acid and 360g (6mol) acetate,
A wherein
14As the definition in the example 2.
100 ℃ after following 30 hours, distillation (100 ℃ 60torr) and filter, obtain 4, the moderately viscous deep green oily matter of 360g (theoretical amount 96%).According to
1H NMR spectrum, this oily matter has following general formula
A wherein
3And A
4As the definition in the compound 2.
Application testing
For the application performance of test by the polysiloxane of modification of the present invention, the product of example 1 to 12 is coated on the different chip carrier (oriented polypropylene, supercalendered paper), under the effect of 1.5Mrad electron beam, solidify.Glue spread respectively is 1.1g/m
2
For comparing experiment, adopt the wide sealing tape of 30mm, in addition, two kinds of sealing tapes have the acrylic binder coating, by commercial goods name Tesa
(R)154 and Tesa
(R)970 can get, and a kind of sealing tape has the rubber adhesive coating, by commercial goods name Tesa
(R)969 can get.
For measuring the unsticking performance, above-mentioned sealing tape is rolled in substrate, store the acrylate sealing tape down for 70 ℃ then, store the rubber sealing tape down for 40 ℃.After 24 hours, sealing tape is shut down from substrate with 180 ° peel angle, measured required power.This power is called as separating force (releaseforce).In addition, also with firmly scraping of thumb, to measure the clinging power of modified polyorganosiloxane to substrate.If clinging power is not enough, can form elastomeric chip (being that what is called is wiped test (" rub-off " test)).
Table
| Modified siloxane | Supercalendered paper | The oriented polypropylene film | |||||||
| Tesa (R) 154 | Tesa (R) 970 | Tesa (R) 969 | Wipe experiment | Tesa (R) 154 | Tesa (R) 970 | Tesa (R) 969 | Wipe experiment | ||
| Example | Acrylate functionalities | ||||||||
| Separating force [N] | Separating force [N] | ||||||||
| 1 | 1.8 | 6 | 10 | 9 | Do not have | 5 | 10 | 9 | Do not have |
| 2* | 5 | 7 | 10 | 9 | Do not have | 6 | 10 | 9 | Do not have |
| 3 | 4 | 5 | 8 | 8 | Do not have | 5 | 8 | 7 | Do not have |
| 4 | 5.6 | 1 | 3 | 3 | Have | 1 | 3 | 2 | Have |
| 5 | 5.6 | 0.05 | 0.2 | 0.15 | Have | 0.05 | 0.2 | 0.15 | Have |
| 6 | 3.6 | 5 | 8 | 8 | Do not have | 5 | 9 | 8 | Do not have |
| 7 | 5.6 | 0.2 | 1 | 0.5 | Have | 0.1 | 0.8 | 0.5 | Have |
| 8 | 6.3 | 0.05 | 0.1 | 0.09 | Have | 0.05 | 0.08 | 0.07 | Have |
| 9 * | 10 | 7 | 1 0 | 9 | Do not have | 6 | 10 | 9 | Do not have |
| 10 | 8 | 5 | 9 | 7 | Do not have | 5 | 8 | 7 | Do not have |
| 11 | 6 | 3 | 8 | 5 | Do not have | 3 | 6 | 5 | Do not have |
| 12 | 4 | 2 | 7 | 4 | Do not have | 2 | 6 | 4 | Do not have |
The mixture of modified siloxane
Example
| 50％ | 1 | 2 | 3 | 3 | Do not have | 2 | 3 | 2 | Do not have |
| 50％ | 8 | ||||||||
| 50％ | 4 | 1 | 2 | 2 | Do not have | 1 | 2 | 1.5 | Do not have |
| 50％ | 8 |
* non-the present invention
From last table, draw, have required application performance by the organopolysiloxane of modification of the present invention.No matter with pure form still in mixture, described organopolysiloxane all can show the gratifying clinging power to respective carrier, fast setting thereon, the different tackiness agent of chemical structure is shown good unsticking, and compare with the prior art situation, also can make it by the substituting group on the identical siloxane backbone of suitable selection to regulate at the chemical property of tackiness agent.
Claims (11)
1. one kind has (methyl) the acrylate-based polysiloxane that connects by the SiC base, and described polysiloxane is following (A) and reaction product (B),
(A) the average following a kind of polysiloxane of general formula
Wherein
R
1Base is identical or different, and represents the low alkyl group or the phenyl of 1 to 4 carbon atom,
R
2Base is
(i) R
1Base, and
(ii) (a) epoxy-functional group and (b) alkyl or the hydrogen of 2 to 10 carbon atoms perhaps are
(iii) group (ii),
Prerequisite is that an average molecule comprises at least 1.8 epoxy group(ing), and described group (ii) comprises 70 to 100% group (ii) (a) and 30 to 0% group (ii) (b),
A is a numerical value 1 to 1,000, and
B is a numerical value 0 to 10,
(B) based on epoxide group, (methyl) vinylformic acid of 0.4 to 0.9 molar weight, and remaining epoxide group with do not react with the monocarboxylic acid of polymerizable double bond.
2. the polysiloxane of claim 1, the monocarboxylic acid of wherein said (B) has 2 to 10 carbon atoms.
3. the polysiloxane of claim 2, wherein said monocarboxylic acid is an acetate.
4. claim 1 or 2 polysiloxane, wherein this subscript a is a numerical value 5 to 200, and this subscript b is a numerical value 0 to 2.
5. claim 1 or 2 polysiloxane, wherein subscript b is 0.
6. claim 1 or 2 polysiloxane, wherein at least 90% R
1Base is a methyl.
7. claim 1 or 2 polysiloxane, wherein epoxy-functional R (ii)
2Base is selected from one group of following group,
With
8. claim 1 or 2 polysiloxane, wherein R
2Basic included alkyl (ii) (b) is selected from the group that following group constitutes: ethyl, propyl group, normal-butyl, isobutyl-, hexyl, octyl group, dodecyl, octadecyl, 2-phenyl propyl and 3-chloropropyl.
9. the unsticking coating composition of a radiation-hardenable mainly is made up of with the radical initiator that is no more than about 5 weight % the polysiloxane of claim 1.
10. the product of a band coating comprises the substrate with a unsticking top coat, and the layer of described unsticking top coat after by the polysiloxane radiation curing of claim 1 or 2 forms.
11. the product of the band coating of claim 10, wherein said layer also additionally comprises a spot of radical initiator.
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|---|---|---|---|
| CN 200610083961 CN101089031A (en) | 2006-06-16 | 2006-06-16 | Polysiloxane with (methyl) propenoic acid ester base and its use |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610083961 CN101089031A (en) | 2006-06-16 | 2006-06-16 | Polysiloxane with (methyl) propenoic acid ester base and its use |
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| Publication Number | Publication Date |
|---|---|
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Family
ID=38942541
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2014029046A1 (en) | 2012-08-22 | 2014-02-27 | Wang Zhijun | Surface control additive for radiation curing system, preparation method therefor and application thereof |
| JP2016153390A (en) * | 2009-09-02 | 2016-08-25 | モメンティブ パフォーマンス マテリアルズ インコーポレイテッド | Silicone modified fatty acids, method of preparation and usage thereof |
| CN107735468A (en) * | 2015-07-06 | 2018-02-23 | 蓝星有机硅法国两合公司 | The method for preparing the organopolysiloxane with (methyl) acrylate-functional groups |
| CN109790416A (en) * | 2016-04-29 | 2019-05-21 | 埃肯有机硅法国简易股份公司 | The preparation method of organopolysiloxane with (methyl) acrylate-functional groups |
| CN115698182A (en) * | 2020-06-12 | 2023-02-03 | 信越化学工业株式会社 | Addition reaction-curable organopolysiloxane composition, and release paper and release film |
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2006
- 2006-06-16 CN CN 200610083961 patent/CN101089031A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016153390A (en) * | 2009-09-02 | 2016-08-25 | モメンティブ パフォーマンス マテリアルズ インコーポレイテッド | Silicone modified fatty acids, method of preparation and usage thereof |
| WO2014029046A1 (en) | 2012-08-22 | 2014-02-27 | Wang Zhijun | Surface control additive for radiation curing system, preparation method therefor and application thereof |
| CN107735468A (en) * | 2015-07-06 | 2018-02-23 | 蓝星有机硅法国两合公司 | The method for preparing the organopolysiloxane with (methyl) acrylate-functional groups |
| CN107735468B (en) * | 2015-07-06 | 2020-10-27 | 蓝星有机硅法国两合公司 | Method for preparing organopolysiloxanes comprising (meth) acrylate functions |
| CN109790416A (en) * | 2016-04-29 | 2019-05-21 | 埃肯有机硅法国简易股份公司 | The preparation method of organopolysiloxane with (methyl) acrylate-functional groups |
| CN115698182A (en) * | 2020-06-12 | 2023-02-03 | 信越化学工业株式会社 | Addition reaction-curable organopolysiloxane composition, and release paper and release film |
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