CN109897141A - A kind of preparation method of the high-intensitive ASA resin of building materials - Google Patents
A kind of preparation method of the high-intensitive ASA resin of building materials Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of ASA resin, the agglomerant technology of preparing of specifically a kind of specific structure, and by the partial size of agglomerant regulation acrylic rubber, and then the method for preparing high-intensitive ASA resin.The technology of the present invention principle is that following two big functions are realized in agglomerant preparation process, and first is to try to guarantee carboxylic acid group on the surface of agglomerant particle, the fusion for facilitating agglomerant particle in this way and being agglomerated between particle between interface；Second is that introducing organosiloxane monomer into agglomerant, make agglomerant latex particle intensity with higher after subsequent fusion.Agglomeration agent emulsion of the present invention be used for polybutylacrylate latex agglomeration, and by after agglomeration latex grafting styrene and acrylonitrile obtain ASA resin, test ASA resin intensity made from the more conventional agglomeration mode of ASA resin mechanical property of the technical program height.
Description
Technical field
The present invention relates to a kind of preparation method of ASA resin, the agglomerant technology of preparing of specifically a kind of specific structure, and
The method for regulating and controlling the partial size of acrylic rubber by the agglomerant, and then preparing high-intensitive ASA resin, it is this to contain siloxanes
The ASA resin of group is particularly suitable for the building materials fields such as coating, concrete, resin tile.
Background technique
The ternary graft copolymer that ASA resin is made of acrylate _ styrene _ acrylonitrile, by BASF Corp. of Germany
Invention, nineteen sixty-eight realize industrialization.ASA resin is using the polyacrylate without double bond structure instead of polybutadiene rubber in ABS
Glue, only wavelength are that 300nm light wave below could play aging action to ASA resin；10 times of ABS high of ASA resin weatherability ratio
Left and right；ASA resin has high impact resistance, high mechanical strength, good heat resistance, chemical resistance simultaneously, so wide
It is general to be applied to the fields such as building materials, automobile, electronic apparatus, outdoor equipment.ASA resin routinely uses emulsion polymerization to prepare acrylic acid
Butyl ester lotion, the graft reaction for then carrying out styrene and acrylonitrile to lotion obtains ASA resin, by acrylic rubber
The physical mechanical property of the control regulation ASA resin of the factors such as emulsion particle diameter, the degree of cross linking, grafting degree.It is similar with ABS resin, ASA
Resin is also a kind of one layer of resin shell of appearance grafting, and inside is the engineering resin material of the excellent combination property of rubber phase.Its
Performance advantage as previously mentioned, but its performance and rubber phase emulsion particle diameter and degree of cross linking correlation it is very big.Liang Tao et al. is " a kind of new
The preparation of the multi-functional agglomerant of type ", it is a kind of new for Material synthesis with butyl acrylate (BA), methacrylic acid and styrene etc.
The multi-functional agglomerant of type.Water-oil factor, initiator amount, different emulsifiers have been inquired into agglomerant partial size, viscosity and solid content
It influences, and the infrared spectrum of agglomerant copolymer is analyzed, finally obtained the optimised process formula of agglomerant.He Jian
Et al. " research that latex agglomeration method prepares big partial size ASA latex " with lauryl sodium sulfate (SDS) be emulsifier, with acrylic acid
Butyl ester (BA), acrylic acid (AA) are main raw material monomer, are prepared for agglomerating latex through multi-step emulsion polymerization method.Then, right with its
PBA latex carries out partial size amplification, studies monomer composition and proportion, agglomerant dosage of latex, time and temperature and agglomeration system
PH value, to agglomeration experiment and PBA latex performance influence.Finally, being prepared for big partial size polyacrylate with latex agglomeration method
(BA)-styrene (St)-acrylonitrile (AN) ternary polymerization (ASA) latex, and have studied the shadow of ASA resin partial size and mechanical property
It rings.
The prior art is mostly to carry out agglomeration to acrylic rubber using macromolecule agglomerant, obtains large grain size latex, attached
Poly- agent be usually used acrylic acid and butyl acrylate copolymerization product, there are the problem of be exactly agglomerant latex agglomeration effect and
Contradictory problems between mechanical property, it is general in order to reach preferable agglomeration effect, carboxylic monomer content in agglomeration agent emulsion
Higher agglomeration effect is better, but latex stable type is poorer, influences polymerisation conversion, and agglomeration agent emulsion is caused to be extremely difficult to be agglomerated
The same mechanical property of latex can inevitably reduce the mechanical property of product in subsequent use process.
Technical solutions according to the invention are to introduce vinylsiloxane monomer, purpose on the basis of existing agglomerant
It is to stick to each other, merge to solve latex particle under agglomeration, interparticle mechanical strength is weaker after mixing, by drawing
The organosiloxane monomer for entering specific structure, the latex particle after making agglomeration form space interpenetrating under the crosslinked action of siloxanes
Network structure enhances the mechanical property of agglomeration mixing latex.Graft copolymerization of the patent CN104755516A containing polysiloxane
Object, resin combination and formed body, thermoplastic resin can be assigned with impact resistance, anti-flammability and colour rendering by providing one kind
Graft copolymer.A kind of graft copolymer containing polysiloxane, the graft copolymer containing polysiloxane are
The graft copolymer containing polysiloxane as made of vinyl monomer and poly organo methane series rubber graft polymeric.This skill
Art scheme improves the performance of ASA resin not by the mode of grafting, but by adjusting the formula and work of agglomerant synthesis
Skill route realizes the improvement to agglomeration lotion mechanical strength.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of high-intensitive ASA resin, specifically design a kind of special attached
Poly- agent mixes the purpose of agglomeration emulsion strength raising to realize, schematic illustration is embodied as shown in Fig. 1 in Figure of description.
The technology of the present invention principle is that following two big function adjustment are realized in agglomerant preparation process, and first is to try to guarantee
Carboxylic acid group is on the surface of agglomerant particle, the fusion that facilitates agglomerant particle in this way and be agglomerated between particle between interface；
Second is that introducing organosiloxane monomer into agglomerant, make agglomerant latex particle intensity with higher after subsequent fusion.
Specifically, a kind of preparation method of high-intensitive ASA resin of the invention, the preparation of mainly a kind of agglomerant and make
With method, comprising the following steps:
1. agglomerant synthesis is by mono alkenyl carboxylic acid lipid monomer (30-80 mass parts), mono alkenyl carboxylic acid type monomer (15-
35 mass parts) and mono alkenyl type siloxane monomer (5-35 mass parts) according to formula mix, with mix monomer gross mass be 100 matter
It measures part to calculate, the additional amount of emulsifier is 0.1-10 mass parts, molecular weight regulator 0.01-0.5 mass parts, the addition of initiator
Amount is 0.1-1 mass parts, and deionized water is 100-200 mass parts.Weigh monomer, emulsifier, molecular weight regulator and deionization
Water reserves the vinyl carboxylic acid monomer of 2/3 mass, reserves the vinylsiloxane class monomer of 1/2 mass, reserves 1/2 mass
The initiator of emulsifier and reserved 1/2 mass, rest materials mix in the reactor, open stirring, control revolving speed and reaction temperature
The initiator of 1/2 mass is added in degree, and after reacting a period of time, remaining mix monomer and emulsifier are born in dropwise addition, is added drop-wise to mixed
When closing 1/3 amount of monomer, the initiator of reserved 1/2 mass is added, obtains agglomeration agent emulsion after reaction.
2. being in mass ratio 1 by agglomeration agent emulsion and polybutylacrylate latex: the ratio metering of (4-10), agglomeration agent emulsion
It is added in the polybutylacrylate latex of stirring, controls temperature and speed of agitator, agglomeration lotion average grain diameter is about after a period of time
350-550nm；
3. the preparation of polybutylacrylate latex is by the crosslinking agent of the butyl acrylate of 100 mass parts, 0.1-2.0 mass parts
Emulsifier mixing with 0.01-0.8 mass parts is distributed in the deionized water of 150 mass parts, and initiator, control reaction temperature is added
Degree and speed of agitator react the lotion obtained after a period of time；
4. the mixed emulsion after agglomeration calculates the quality of grafted monomers according to butt amount, conventional grafted monomers are dry glue amount
20%-80%, styrene and acrylonitrile monemer (the two ratio is 3: 1) is weighed after calculating, gross mass is 100 mass parts, is added
Enter emulsifier 0.2-2 mass parts, molecular weight regulator 0.01-0.8 mass parts, organic peroxy is added in 200 mass parts of deionization
Object initiator controls reaction temperature and speed of agitator, obtains ASA resin after reacting a period of time, through cohesion, washing, drying, is total to
The process of mixed granulation etc. obtains product, by the mechanical property of standard testing ASA resin.
Agglomerant of the present invention is by mono alkenyl carboxylic acid esters monomer, monoene carboxylic acid type monomer, monoene type siloxane
Monomer is by made from emulsion free-radical copolymerization；
Wherein carboxylic acid lipid monomer can be methyl acrylate, ethyl acrylate, butyl acrylate, amyl acrylate, first
Base methyl acrylate, ethyl methacrylate, butyl methacrylate, pentylmethacrylate etc. have the list of similar structure
Body, preferably butyl acrylate；
Monoene carboxylic acid type monomer can be acrylic acid, methacrylic acid, ethylacrylic acid, butenoic acid, methacrylate, ethylene
The monomer containing monoene and carboxylic acid group such as yl benzoic acid, hexenoic acid, preferably methacrylic acid；
Monoene siloxanyl monomers structural formula is as follows:
Wherein:
R1Unsaturated olefin aliphatic segment containing no less than 2 carbon, can be vinyl, acrylic, isopropyl alkene
Base, isopentene group, 3- pentenyl, 6- octenyl, trimethyl-ethylene base, 1- heptenyl, methacryloxypropyl, methyl-prop
Alkene acyloxy, preferred vinyl；
R2、R3And R4It can be the alkoxy containing no less than 1 carbon, the aryloxy group of no less than 6 carbon can be methoxy
Base, ethyoxyl, propoxyl group, isopropoxy, n-butoxy, hexyloxy, amoxy, positive oxygroup in heptan, different octyloxy, positive nonyl epoxide,
Phenoxy group, chlorophenoxy, allyloxy, benzyloxy, acetoxyl group, trimethylsiloxy group, preferably methoxyl group, ethyoxyl；R2、R3
And R4In three groups preferably there are two be alkoxy, remaining next group can also be containing be no less than 1 carbon saturation segment
Or cyclic alkane, aromatic hydrocarbon；It is preferred that methyl, ethyl；
Purpose is hydrolyzed by alkoxy, thus formation-O-Si- spatial network knot in the rubbery system after agglomeration
Structure, to play reinforcing effect to ASA base latex；If only one alkoxy in organosiloxane monomer, formation-O-
Si- spacial framework ability is poor, and the effect of reinforcement is poor.
Monoene siloxanyl monomers of the present invention can be vinyltriethoxysilane, vinyl diethoxy-second
Base silane, vinyltrimethoxysilane, two amoxys of vinyl-hexyl silane, two n-butoxyethyl silane of isopropenyl
Deng preferred vinyl triethoxysilane；
Emulsifier of the present invention can be neopelex, lauryl sodium sulfate, saturated fatty acid sodium,
The basic potassium sulfonate of dodecane, dodecyl sulphate potassium, saturation rosin calculate the anion emulsifiers, preferably dodecyl benzene sulfonic acid such as potassium
Sodium, lauryl sodium sulfate；
Initiator of the present invention can be potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate etc., preferably potassium peroxydisulfate；
Molecular weight regulator of the present invention can be tert-dodecyl mercaptan, DDM dodecyl mercaptan etc. suitable for emulsion free-radical
The auxiliary agent of the chain transfer of polymerization system, preferably tert-dodecyl mercaptan；
The preparation process of agglomerant of the present invention require be by mono alkenyl carboxylic acid lipid monomer 30-80 mass parts, it is excellent
Select 70 parts；Mono alkenyl carboxylic acid type monomer's 15-35 mass parts, preferably 20 parts；Mono alkenyl type siloxane monomer 5-35 mass parts, preferably
10 parts；It is mixed according to formula, is the calculating of 100 mass parts with mix monomer gross mass, the additional amount of emulsifier is 0.1-10 mass
Preferably 0.8 part of part, preferably 0.05 part of molecular weight regulator 0.01-0.5 mass parts, the additional amount of initiator is 0.1-1 mass parts
It is preferred that 0.5 part, deionized water is preferably 150 parts of 100-200 mass parts.Weigh monomer, emulsifier, molecular weight regulator and go from
Sub- water reserves the vinyl carboxylic acid monomer of 2/3 mass, reserves the vinylsiloxane class monomer of 1/2 mass, reserves 1/2 mass
Emulsifier and reserved 1/2 mass initiator, rest materials mix in the reactor, open stirring, control revolving speed 100-
The initiator of 1/2 mass is added in 500rpm and 45-80 DEG C of reaction temperature, and after reacting 20-50min, remaining mixing is born in dropwise addition
Monomer and emulsifier when being added drop-wise to 1/3 amount of mix monomer, are added the initiator of reserved 1/2 mass, are obtained after reaction
Agglomeration agent emulsion.
Agglomeration agent emulsion of the present invention is used for the agglomeration of polybutylacrylate latex, and by the latex grafting benzene after agglomeration
Ethylene and acrylonitrile obtain ASA resin, test made from the more conventional agglomeration mode of ASA resin mechanical property of the technical program
ASA resin intensity is high.
A kind of preparation method of specific high-intensitive ASA resin is, a kind of prefabricated agglomerant is simultaneously applied to as follows
Butyl acrylate rubber agglomeration, grafting prepare ASA resin.The preparation of polybutylacrylate latex is by the acrylic acid of 100 mass parts
The emulsifier mixing of butyl ester, the crosslinking agent diallyl phthalate of 1.0 mass parts and 0.3 mass parts is distributed to 150 mass
In the deionized water of part, initiator potassium persulfate, 45-80 DEG C of control temperature and speed of agitator 100-500rpm is added, reacts 50-
The lotion obtained after 150min, wherein reaction raw materials can be added using segmentation and wait different modes；By agglomeration agent emulsion and propylene
Acid butyl ester lotion is 1: 4 ratio metering in mass ratio, and agglomeration agent emulsion is added in the polybutylacrylate latex of stirring, control temperature
45-80 DEG C and speed of agitator 100-500rpm is spent, agglomeration lotion average grain diameter is about 350-550nm after 50min；It is mixed after agglomeration
The quality that lotion calculates grafted monomers according to butt amount is closed, conventional grafted monomers are the 60% of dry glue amount, weigh benzene after calculating
Ethylene and acrylonitrile monemer (the two ratio is 3: 1), gross mass is 100 mass parts, and 1.5 mass parts of emulsifier, molecular weight is added
0.3 mass parts of organic peroxide evocating agent lauroyl peroxide are added in 0.06 mass parts of regulator, 200 mass parts of deionization,
Control 50 DEG C of reaction temperature and speed of agitator 400rpm, obtain ASA resin after reacting 30-80min, through cohesion, washing, drying,
The process that granulation etc. is blended obtains product, by the mechanical property of standard testing ASA resin.
Detailed description of the invention
Fig. 1 is high-intensitive ASA resin agglomeration schematic illustration.
Specific embodiment
Material auxiliary agent needed for present invention specific implementation is as described below:
(1) methacrylic acid, butyl acrylate, SILVER REAGENT are commercially available；Vinyltriethoxysilane, vinyl diethyl
Ethoxysilane, vinyl trimethoxy siloxanes, SILVER REAGENT, Shanghai Hui Pu siloxanes Co., Ltd；
(2) acrylonitrile, styrene, lauryl sodium sulfate, tert-dodecyl mercaptan, potassium peroxydisulfate, deionized water, industry
Grade, it is commercially available；
(3) other are SILVER REAGENT without the reagent referred to, commercially available.
Mechanics Performance Testing is carried out according to corresponding national standard.
Embodiment 1:
By Butyl Acrylate Monomer 70g, methacrylic acid monomer 15g；Vinyltrimethoxysilane monomer 15g；According to
The additional amount of formula mixing, emulsifier sodium lauryl sulfate is 0.2g, and molecular weight regulator tert-dodecyl mercaptan 0.03g draws
The additional amount for sending out agent potassium peroxydisulfate is 0.5g, deionized water 150g.Weigh monomer, emulsifier, molecular weight regulator and go from
Sub- water reserves the methacrylic acid monomer of 10g, reserves 7.5g vinyltrimethoxysilane, reserves the emulsifier of 0.1g and pre-
The initiator of 0.25g is stayed, rest materials mix in the reactor, and stirring is opened, revolving speed 500rpm and 60 DEG C of reaction temperature are controlled,
The initiator of 0.25g is added, after reacting 20min, reserved mix monomer and emulsifier is added dropwise, is added drop-wise to reserved mix monomer 1/
When 3 amount, the initiator of reserved 1/2 mass is once added, obtains agglomeration agent emulsion after reaction.
Agglomeration agent emulsion is used for the agglomeration of polybutylacrylate latex, and by the latex grafting styrene and acrylonitrile after agglomeration
ASA resin is obtained, the process through cohesion, washing, drying, blending granulation etc. obtains product, by the mechanics of standard testing ASA resin
Performance.
Comparative example 1: vinyltrimethoxysilane monomer is not added
With the identical formula of embodiment and technique, difference is that vinyltrimethoxysilane is not added.By acrylic acid
Butyl ester monomer 70g, methacrylic acid monomer 15g；Vinyltrimethoxysilane monomer 0g；It is mixed according to formula, emulsifier ten
The additional amount of sodium dialkyl sulfate is 0.2g, molecular weight regulator tert-dodecyl mercaptan 0.03g, the addition of initiator potassium persulfate
Amount is 0.5g, deionized water 150g.Monomer, emulsifier, molecular weight regulator and deionized water are weighed, the methyl of 10g is reserved
Acrylic monomers reserves 0g vinyltrimethoxysilane, reserves the emulsifier of 0.1g and the initiator of reserved 0.25g, remaining
Material mixes in the reactor, opens stirring, controls revolving speed 500rpm and 60 DEG C of reaction temperature, the initiator of 0.25g is added, instead
After answering 20min, reserved mix monomer and emulsifier is added dropwise, when being added drop-wise to reserved 1/3 amount of mix monomer, once adds pre-
The initiator of 1/2 mass is stayed, obtains agglomeration agent emulsion after reaction.
Agglomeration agent emulsion is used for the agglomeration of polybutylacrylate latex, and by the latex grafting styrene and acrylonitrile after agglomeration
ASA resin is obtained, the process through cohesion, washing, drying, blending granulation etc. obtains product, by the mechanics of standard testing ASA resin
Performance.
Embodiment 2: intensity is more slightly lower than 1
By Butyl Acrylate Monomer 80g, ethyl propylene acid monomers 15g；Vinyltriethoxysilane monomer 5g；According to matching
Side's mixing, the additional amount of emulsifier sodium lauryl sulfate are 2g, molecular weight regulator tert-dodecyl mercaptan 0.1g, initiator mistake
The additional amount of potassium sulfate is 0.7g, deionized water 160g.Monomer, emulsifier, molecular weight regulator and deionized water are weighed, in advance
It stays the ethyl propylene acid monomers of 10g, reserves 2.5g vinyltriethoxysilane, reserve the emulsifier and reserved 0.35g of 1g
Initiator, rest materials mix in the reactor, open stirring, control revolving speed 300rpm and 60 DEG C of reaction temperature, 0.35g is added
Initiator, react 30min after, reserved mix monomer and emulsifier is added dropwise, be added drop-wise to reserved 1/3 amount of mix monomer when
It waits, once adds the initiator of reserved 1/2 mass, obtain agglomeration agent emulsion after reaction.
Agglomeration agent emulsion is used for the agglomeration of polybutylacrylate latex, and by the latex grafting styrene and acrylonitrile after agglomeration
ASA resin is obtained, the process through cohesion, washing, drying, blending granulation etc. obtains product, by the mechanics of standard testing ASA resin
Performance.
Comparative example 2: acrylic acid ester emulsion, direct agglomeration, then the lotion after agglomeration carries out graft reaction, reaction process
Middle addition vinyltriethoxysilane, this intensity are more slightly higher than a upper comparative example；
By Butyl Acrylate Monomer 80g, ethyl propylene acid monomers 15g；Vinyltriethoxysilane monomer 0g；According to matching
Side's mixing, the additional amount of emulsifier sodium lauryl sulfate are 2g, molecular weight regulator tert-dodecyl mercaptan 0.1g, initiator mistake
The additional amount of potassium sulfate is 0.7g, deionized water 160g.Monomer, emulsifier, molecular weight regulator and deionized water are weighed, in advance
The ethyl propylene acid monomers of 10g are stayed, 0g vinyltriethoxysilane is reserved, reserve the emulsifier of 1g and drawing for reserved 0.35g
Agent is sent out, rest materials mix in the reactor, open stirring, control revolving speed 300rpm and 60 DEG C of reaction temperature, be added 0.35g's
Reserved mix monomer and emulsifier is added dropwise after reacting 30min in initiator, when being added drop-wise to reserved 1/3 amount of mix monomer,
The initiator for once adding reserved 1/2 mass, obtains agglomeration agent emulsion after reaction.
Agglomeration agent emulsion is used for the agglomeration of polybutylacrylate latex, and by the latex grafting styrene and propylene after agglomeration
Nitrile, while grafting vinyl Ethoxysilane, obtain ASA resin, and the process through cohesion, washing, drying, blending granulation etc. obtains
Product, by the mechanical property of standard testing ASA resin.
Embodiment 3: the strong reinforcing effect intensity of agglomeration effect is higher than 1
By Butyl Acrylate Monomer 30g, methacrylic acid monomer 35g；Vinyltriethoxysilane monomer 35g；According to
Formula mixing, the additional amount of emulsifier sodium lauryl sulfate are 6g, molecular weight regulator tert-dodecyl mercaptan 0.31g, are caused
The additional amount of agent potassium peroxydisulfate is 0.9g, deionized water 190g.Weigh monomer, emulsifier, molecular weight regulator and deionization
Water reserves the methacrylic acid monomer of 52g, reserves 18g vinyltriethoxysilane, reserves the emulsifier of 3g and reserves
The initiator of 0.45g, rest materials mix in the reactor, open stirring, control revolving speed 500rpm and 65 DEG C of reaction temperature, add
Enter the initiator of 0.45g, after reacting 50min, reserved mix monomer and emulsifier is added dropwise, is added drop-wise to reserved mix monomer 1/3
When amount, the initiator of reserved 1/2 mass is once added, obtains agglomeration agent emulsion after reaction.
Agglomeration agent emulsion is used for the agglomeration of polybutylacrylate latex, and by the latex grafting styrene and acrylonitrile after agglomeration
ASA resin is obtained, the process through cohesion, washing, drying, blending granulation etc. obtains product, by the mechanics of standard testing ASA resin
Performance.
Comparative example 3: being not added methacrylic acid monomer, and part is supplied by butyl acrylate, does not have agglomeration effect, mechanical property
It is poorer than comparative example 2
Butyl Acrylate Monomer 65g, methacrylic acid monomer 0g；Vinyltriethoxysilane monomer 35g；According to formula
Mixing, the additional amount of emulsifier sodium lauryl sulfate are 6g, molecular weight regulator tert-dodecyl mercaptan 0.31g, initiator mistake
The additional amount of potassium sulfate is 0.9g, deionized water 190g.Monomer, emulsifier, molecular weight regulator and deionized water are weighed, in advance
The methacrylic acid monomer of 0g is stayed, 18g vinyltriethoxysilane is reserved, reserves the emulsifier of 3g and drawing for reserved 0.45g
Agent is sent out, rest materials mix in the reactor, open stirring, control revolving speed 500rpm and 65 DEG C of reaction temperature, be added 0.45g's
Reserved mix monomer and emulsifier is added dropwise after reacting 50min in initiator, when being added drop-wise to reserved 1/3 amount of mix monomer,
The initiator for once adding reserved 1/2 mass, obtains agglomeration agent emulsion after reaction.
Agglomeration agent emulsion is used for the agglomeration of polybutylacrylate latex, and by the latex grafting styrene and acrylonitrile after agglomeration
ASA resin is obtained, the process through cohesion, washing, drying, blending granulation etc. obtains product, by the mechanics of standard testing ASA resin
Performance.
Embodiment 4: intensity is slightly stronger than 1
Butyl Acrylate Monomer 50g, methacrylic acid monomer 25g；Vinyltributoxysilane monomer 25g；According to matching
Side's mixing, the additional amount of emulsifier neopelex are 10g, molecular weight regulator tert-dodecyl mercaptan 0.25g, are caused
The additional amount of agent potassium peroxydisulfate is 0.6g, deionized water 120g.Weigh monomer, emulsifier, molecular weight regulator and deionization
Water reserves the methacrylic acid monomer of 16g, reserves 13g vinyltributoxysilane, reserves the emulsifier and reserved 0.3g of 5g
Initiator, rest materials mix in the reactor, open stirring, control revolving speed 400rpm and 58 DEG C of reaction temperature, be added
The initiator of 0.3g is added dropwise reserved mix monomer and emulsifier, is added drop-wise to reserved 1/3 amount of mix monomer after reacting 45min
When, the initiator of reserved 1/2 mass is once added, obtains agglomeration agent emulsion after reaction.
Agglomeration agent emulsion is used for the agglomeration of polybutylacrylate latex, and by the latex grafting styrene and acrylonitrile after agglomeration
ASA resin is obtained, the process through cohesion, washing, drying, blending granulation etc. obtains product, by the mechanics of standard testing ASA resin
Performance.
Comparative example 4: three butoxy silane of ethyl does not polymerize
Butyl Acrylate Monomer 50g, methacrylic acid monomer 25g；Three butoxy silane monomer 25g of ethyl；According to formula
Mixing, the additional amount of emulsifier neopelex are 10g, molecular weight regulator tert-dodecyl mercaptan 0.25g, initiator
The additional amount of potassium peroxydisulfate is 0.6g, deionized water 120g.Monomer, emulsifier, molecular weight regulator and deionized water are weighed,
The methacrylic acid monomer of reserved 16g, reserves three butoxy silane of 13g ethyl, reserves the emulsifier of 5g and drawing for reserved 0.3g
Agent is sent out, rest materials mix in the reactor, open stirring, control revolving speed 400rpm and 58 DEG C of reaction temperature, be added 0.3g's
Reserved mix monomer and emulsifier is added dropwise after reacting 45min in initiator, when being added drop-wise to reserved 1/3 amount of mix monomer,
The initiator for once adding reserved 1/2 mass, obtains agglomeration agent emulsion after reaction.
Agglomeration agent emulsion is used for the agglomeration of polybutylacrylate latex, and by the latex grafting styrene and acrylonitrile after agglomeration
ASA resin is obtained, the process through cohesion, washing, drying, blending granulation etc. obtains product, by the mechanics of standard testing ASA resin
Performance.
Embodiment 5:
Butylmethacrylate monomer 50g, methacrylic acid monomer 35g；Vinyltrimethoxysilane monomer 15g；It presses
It is mixed according to formula, the additional amount of emulsifier neopelex is 0.1g, molecular weight regulator tert-dodecyl mercaptan
0.01g, the additional amount of initiator potassium persulfate are 0.1g, deionized water 100g.Weigh monomer, emulsifier, molecular-weight adjusting
Agent and deionized water reserve the methacrylic acid monomer of 24g, reserve 8g vinyltrimethoxysilane, reserve the emulsification of 0.05g
The initiator of agent and reserved 0.05g, rest materials mix in the reactor, open stirring, control revolving speed 100rpm and reaction temperature
The initiator of 0.05g is added in 55 DEG C of degree, and after reacting 50min, reserved mix monomer and emulsifier is added dropwise, and is added drop-wise to reserved mixed
When closing 1/3 amount of monomer, the initiator of reserved 1/2 mass is once added, obtains agglomeration agent emulsion after reaction.
Agglomeration agent emulsion is used for the agglomeration of polybutylacrylate latex, and by the latex grafting styrene and acrylonitrile after agglomeration
ASA resin is obtained, the process through cohesion, washing, drying, blending granulation etc. obtains product, by the mechanics of standard testing ASA resin
Performance.
Comparative example 5: the polymerization of isoprene acid butyl ester, weatherability are poor
Isoprene acid butyl ester monomer 50g, methacrylic acid monomer 35g；Vinyltrimethoxysilane monomer 15g；It presses
It is mixed according to formula, the additional amount of emulsifier neopelex is 0.1g, molecular weight regulator tert-dodecyl mercaptan
0.01g, the additional amount of initiator potassium persulfate are 0.1g, deionized water 100g.Weigh monomer, emulsifier, molecular-weight adjusting
Agent and deionized water reserve the methacrylic acid monomer of 24g, reserve 8g vinyltrimethoxysilane, reserve the emulsification of 0.05g
The initiator of agent and reserved 0.05g, rest materials mix in the reactor, open stirring, control revolving speed 100rpm and reaction temperature
The initiator of 0.05g is added in 55 DEG C of degree, and after reacting 50min, reserved mix monomer and emulsifier is added dropwise, and is added drop-wise to reserved mixed
When closing 1/3 amount of monomer, the initiator of reserved 1/2 mass is once added, obtains agglomeration agent emulsion after reaction.
Agglomeration agent emulsion is used for the agglomeration of polybutylacrylate latex, and by the latex grafting styrene and acrylonitrile after agglomeration
ASA resin is obtained, the process through cohesion, washing, drying, blending granulation etc. obtains product, by the mechanics of standard testing ASA resin
Performance.
Embodiment 6:
By Butyl Acrylate Monomer 70g, methacrylic acid monomer 20g；Vinyltrimethoxysilane monomer 10g；According to
The additional amount of formula mixing, emulsifier sodium lauryl sulfate is 0.2g, and molecular weight regulator tert-dodecyl mercaptan 0.03g draws
The additional amount for sending out agent potassium peroxydisulfate is 0.5g, deionized water 150g.Weigh monomer, emulsifier, molecular weight regulator and go from
Sub- water reserves the methacrylic acid monomer of 14g, reserves 5g vinyltrimethoxysilane, reserves the emulsifier of 0.1g and reserves
The initiator of 0.25g, rest materials mix in the reactor, open stirring, control revolving speed 500rpm and 60 DEG C of reaction temperature, add
Enter the initiator of 0.25g, after reacting 20min, reserved mix monomer and emulsifier is added dropwise, is added drop-wise to reserved mix monomer 1/3
When amount, the initiator of reserved 1/2 mass is once added, obtains agglomeration agent emulsion after reaction.
Agglomeration agent emulsion is used for the agglomeration of polybutylacrylate latex, and by the latex grafting styrene and acrylonitrile after agglomeration
ASA resin is obtained, the process through cohesion, washing, drying, blending granulation etc. obtains product, by the mechanics of standard testing ASA resin
Performance.
Comparative example 6: agglomerant is done with acetic acid, mechanical property is low
Acetic acid does agglomeration of the agglomerant for polybutylacrylate latex, and by the latex grafting styrene and propylene after agglomeration
Nitrile obtains ASA resin, and the process through cohesion, washing, drying, blending granulation etc. obtains product, by the power of standard testing ASA resin
Learn performance.
ASA resin mechanical property in 1 embodiment and comparative example of table
Claims (22)
1. a kind of preparation method of high-intensitive ASA resin of the invention, mainly a kind of preparation and application of agglomerant, packet
Include following steps: agglomerant synthesis is by mono alkenyl carboxylic acid lipid monomer (30-80 mass parts), mono alkenyl carboxylic acid type monomer (15-
35 mass parts) and mono alkenyl type siloxane monomer (5-35 mass parts) according to formula mix, with mix monomer gross mass be 100 matter
It measures part to calculate, the additional amount of emulsifier is 1-10 mass parts, molecular weight regulator 0.01-0.5 mass parts, the additional amount of initiator
For 0.1-1 mass parts, deionized water is 100-200 mass parts.Monomer, emulsifier, molecular weight regulator and deionized water are weighed,
The vinyl carboxylic acid monomer of reserved 2/3 mass, reserves the vinylsiloxane class monomer of 1/2 mass, reserves the emulsification of 1/2 mass
The initiator of agent and reserved 1/2 mass, rest materials mix in the reactor, open stirring, control revolving speed and reaction temperature, add
Enter the initiator of 1/2 mass, after reacting a period of time, remaining mix monomer and emulsifier are born in dropwise addition, and it is single to be added drop-wise to mixing
When 1/3 amount of body, the initiator of reserved 1/2 mass is added, obtains agglomeration agent emulsion after reaction.Agglomeration agent emulsion is used
In the agglomeration of polybutylacrylate latex, and by after agglomeration latex grafting styrene and acrylonitrile obtain a kind of high intensity ASA tree
Rouge.
2. agglomerant as described in claim 1 is by mono alkenyl carboxylic acid esters monomer, monoene carboxylic acid type monomer, monoene siloxanes
Class monomer is by made from emulsion free-radical copolymerization.
3. the carboxylic acid lipid monomer as described in claim 1,2 can be methyl acrylate, ethyl acrylate, butyl acrylate,
Amyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, pentylmethacrylate etc. have
The monomer of similar structure, preferably butyl acrylate.
4. the monoene carboxylic acid type monomer as described in claim 1,2 can be acrylic acid, methacrylic acid, ethylacrylic acid, fourth
The monomer containing monoene and carboxylic acid group such as olefin(e) acid, methacrylate, vinyl benzoic acid, hexenoic acid, preferably methacrylic acid.
5. the monoene siloxanyl monomers structural formula as described in claim 1,2 is as follows:
Wherein: R1Unsaturated olefin aliphatic segment containing no less than 2 carbon, can be vinyl, acrylic, isopropyl alkene
Base, isopentene group, 3- pentenyl, 6- octenyl, trimethyl-ethylene base, 1- heptenyl, methacryloxypropyl, methyl-prop
Alkene acyloxy, preferred vinyl；R2、R3And R4It can be the alkoxy containing no less than 1 carbon, the fragrant oxygen of no less than 6 carbon
Base can be methoxyl group, ethyoxyl, propoxyl group, isopropoxy, n-butoxy, hexyloxy, amoxy, positive oxygroup in heptan, different pungent oxygen
Base, positive nonyl epoxide, phenoxy group, chlorophenoxy, allyloxy, benzyloxy, acetoxyl group, trimethylsiloxy group, preferably methoxyl group,
Ethyoxyl；R2、R3And R4In three groups preferably there are two be alkoxy, remaining next group can also be containing be no less than 1 carbon
Saturation segment or cyclic alkane, aromatic hydrocarbon；It is preferred that methyl, ethyl.
6. the monoene siloxanyl monomers as described in claim 1,2,5 can be vinyltriethoxysilane, vinyl diethyl
Oxygroup-ethylsilane, vinyltrimethoxysilane, two amoxys of vinyl-hexyl silane, two n-butoxy second of isopropenyl
Base silane etc., preferred vinyl triethoxysilane.
7. emulsifier as described in claim 1 can be neopelex, lauryl sodium sulfate, saturated fatty acid
The basic potassium sulfonate of sodium, dodecane, dodecyl sulphate potassium, saturation rosin calculate the anion emulsifiers, preferably detergent alkylate such as potassium
Sodium sulfonate, lauryl sodium sulfate.
8. initiator as described in claim 1 can be potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate etc., preferably potassium peroxydisulfate.
9. molecular weight regulator as described in claim 1, which can be tert-dodecyl mercaptan, DDM dodecyl mercaptan etc., is suitable for lotion certainly
By the auxiliary agent of the chain transfer of base polymerization system, preferably tert-dodecyl mercaptan.
10. mono alkenyl carboxylic acid lipid monomer 30-80 mass parts as described in claim 1, preferably 70 parts.
11. mono alkenyl carboxylic acid type monomer 15-35 mass parts as described in claim 1, preferably 20 parts.
12. mono alkenyl type siloxane monomer 5-35 mass parts as described in claim 1, preferably 10 parts.
13. it is as described in claim 1, it is the calculating of 100 mass parts with mix monomer gross mass, the additional amount of emulsifier is 0.1-
Preferably 0.8 part of 10 mass parts.
14. it is as described in claim 1, it is the calculating of 100 mass parts, molecular weight regulator 0.01-0.5 with mix monomer gross mass
Preferably 0.05 part of mass parts.
15. it is as described in claim 1, it is the calculating of 100 mass parts with mix monomer gross mass, the additional amount of initiator is 0.1-
Preferably 0.5 part of 1 mass parts.
16. it is as described in claim 1, it is the calculating of 100 mass parts with mix monomer gross mass, deionized water is 100-200 matter
Preferably 150 parts of part of amount.
17. reagent as described in claim 1 weighs, the vinyl carboxylic acid monomer of reserved 2/3 mass is needed, 1/2 mass is reserved
Vinylsiloxane class monomer, reserve the emulsifier of 1/2 mass and the initiator of reserved 1/2 mass.
18. process conditions as described in claim 1 are control revolving speed 100-500rpm and 45-80 DEG C of reaction temperature.
19. the initial initiator amount as described in claim 1,17 is the initiator that 1/2 mass is added.
20. as described in claim 1,17 agglomerant emulsification radical reaction 20-50min after be added dropwise remaining mix monomer and
Emulsifier when being added drop-wise to 1/3 amount of mix monomer, adds the initiator of reserved 1/2 mass.
21. agglomerant as described in claim 1 is mixed with butyl acrylate) latex carries out agglomeration reaction, butt ratio is 1:
(1-4) preferably 1: 4.
22. the agglomerant preparation and its use as described in the claims are in conventional radical polymerization lotion macromolecule agglomerant
Under conditions of the mechanism of action, however it is not limited to the normal condition.
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| CN110776597A (en) * | 2019-11-15 | 2020-02-11 | 杭州海维特化工科技有限公司 | ASA plastic film ink resin and preparation method thereof |
| CN111234114A (en) * | 2020-03-17 | 2020-06-05 | 中国核工业中原建设有限公司 | Preparation method of polymer latex for improving impermeability of cement-based concrete |
| CN111348867A (en) * | 2020-03-16 | 2020-06-30 | 中国核工业中原建设有限公司 | Preparation method of modified ASA resin concrete |
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| CN110256774A (en) * | 2019-07-04 | 2019-09-20 | 浙江科普特新材料有限公司 | A kind of high durable bloom white is exempted to spray ASA material and preparation method thereof |
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| CN111348867B (en) * | 2020-03-16 | 2021-06-15 | 中国核工业中原建设有限公司 | Preparation method of modified ASA resin concrete |
| CN111234114A (en) * | 2020-03-17 | 2020-06-05 | 中国核工业中原建设有限公司 | Preparation method of polymer latex for improving impermeability of cement-based concrete |
| CN111234114B (en) * | 2020-03-17 | 2021-06-15 | 中国核工业中原建设有限公司 | Preparation method of polymer latex for improving impermeability of cement-based concrete |
| CN111607034A (en) * | 2020-05-13 | 2020-09-01 | 中国核工业中原建设有限公司 | Preparation method of ASA resin cementing material for resin concrete |
| CN111607034B (en) * | 2020-05-13 | 2022-04-05 | 中国核工业中原建设有限公司 | Preparation method of ASA resin cementing material for resin concrete |
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