CN110283265A - Styrene-vinyl versatate acrylate class copolymer emulsion and preparation method - Google Patents
Styrene-vinyl versatate acrylate class copolymer emulsion and preparation method Download PDFInfo
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- CN110283265A CN110283265A CN201910603974.1A CN201910603974A CN110283265A CN 110283265 A CN110283265 A CN 110283265A CN 201910603974 A CN201910603974 A CN 201910603974A CN 110283265 A CN110283265 A CN 110283265A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
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- C09D125/14—Copolymers of styrene with unsaturated esters
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J125/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
- C09J125/02—Homopolymers or copolymers of hydrocarbons
- C09J125/04—Homopolymers or copolymers of styrene
- C09J125/08—Copolymers of styrene
- C09J125/14—Copolymers of styrene with unsaturated esters
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Abstract
The invention discloses a kind of styrene-vinyl versatate acrylate class copolymer emulsions and preparation method, this method to include: step 1, weighing each raw material in proportion；Step 2, it takes polymerized monomer styrene, tertiary ethylene carbonate, esters of acrylic acid to be added in pre-emulsification kettle, emulsifier is added, carries out pre-emulsification in deionized water, obtains pre-emulsion；Step 3, it by pre-emulsion under conditions of heating and thermal insulation, is added dropwise in the deionized water containing emulsifier using initiator, is post-processed after reaction with oxidation-reduction method；Step 4, copolymer emulsion is adjusted into pH value, then vacuumize removing residual monomer, after filtering to obtain the final product.The present invention also provides the styrene-vinyl versatate acrylate class copolymer emulsions prepared by this method.There is copolymer emulsion prepared by the present invention the hardness of styrene-acrylic emulsion to have tertiary acrylic emulsion toughness again, be a kind of adhesive force it is strong, just in soft synthetic emulsion, can be applied to high-grade coating and adhesive.
Description
Technical field
The present invention relates to a kind of copolymer emulsion and preparation methods, and in particular, to a kind of styrene-tertiary ethylene carbonate-
Acrylate copolymer emulsion and preparation method.
Background technique
Monomer is dispersed into the polymerization of emulsion state, referred to as emulsion polymerization by emulsifier in water.Conventional emulsion polymerization system
It is mainly made of monomer, water, water soluble starter, four part of water soluble emulsifier, the formula industrially applied then is wanted complicated and obtained
It is more.Emulsion polymerization is often combined polymerization, in addition to main monomer, it is also possible to have second and third monomer.
The advantages of emulsion polymerization: (1) water as medium, inexpensive safety.Viscosity of latex is low, be conducive to Stirring heat transfer, conveying and
Continuous production；(2) rate of polymerization is fast, while molecular weight of product is high, and polymerization can carry out at a lower temperature；(3) be conducive to
The production of latex directly used with environmental-friendly product, such as water and milk paint, binder, paper, leather, fabric-treating agent etc..
The shortcomings that emulsion polymerization: when (1) needing solid product, lotion need to be through the processes such as cohesion, washing, dehydration, drying, higher cost；
(2) there are the impurity such as emulsifier in product, it is difficult to and it is completely cleared, damage electrical property etc..
Introduce the acrylic emulsion system of hard monomer styrene, referred to as styrene-acrylate emulsion, referred to as benzene
Acrylic emulsion.Styrene-acrylic emulsion (styrene-acrylate emulsion) is to be obtained by styrene and acrylate monomer through emulsion copolymerization.Benzene
Acrylic emulsion is the ten big non-crosslinked types studied more system and the world today in emulsion polymerization and have essential industry application value
One of lotion.Styrene-acrylic emulsion has very extensive purposes, is now mainly used as building as a kind of important intermediate chemical products
Coating, metal surface latex paint, floor coating, paper adhesives, adhesive etc..According to technique and the difference of function, phenylpropyl alcohol
There are many kinds of classes for lotion.
It is the copolymer emulsion of another high comprehensive performance using tertiary ethylene carbonate as the copolymer emulsion of monomer.But by
In styrene, poly- rate differs greatly unexpectedly with tertiary ethylene carbonate, and the two can not be copolymerized into water stability lotion, and general
It can be copolymerized in a solvent, form copolymer.
Summary of the invention
The object of the present invention is to provide a kind of styrene, tertiary ethylene carbonate, acrylic compounds ternary copolymer emulsion and preparations
Method can form copolymer in water, which has the features such as at low cost, feasibility is high.
In order to achieve the above object, the present invention provides a kind of styrene-vinyl versatate acrylate class copolymerization creams
The preparation method of liquid, wherein the method includes: step 1, each raw material is weighed in proportion；Step 2, styrene polymerization list is taken
Body, tertiary ethylene carbonate polymerized monomer, esters of acrylic acid polymerization monomer are added in pre-emulsification kettle, emulsifier are added, in deionization
Pre-emulsification is carried out in water, obtains pre-emulsion；Step 3, the resulting pre-emulsion of step 2 is being contained under conditions of heating and thermal insulation
It is added dropwise in the deionized water of emulsifier using initiator, after being carried out with oxidation-reduction method to resulting copolymer emulsion after reaction
Processing；Step 4, the resulting copolymer emulsion of step 3 is adjusted into pH value, then vacuumize removing residual monomer, after filtering to obtain the final product
To styrene-vinyl versatate acrylate class copolymer emulsion.
The preparation method of above-mentioned styrene-vinyl versatate acrylate class copolymer emulsion, wherein the step
The weight ratio of styrene polymerization monomer, tertiary ethylene carbonate polymerized monomer, esters of acrylic acid polymerization monomer in rapid 2 is 100:
(15~35): (4~10).
The preparation method of above-mentioned styrene-vinyl versatate acrylate class copolymer emulsion, wherein described third
Olefin(e) acid esters polymerized monomer includes butyl acrylate, butyl methacrylate, hydroxypropyl acrylate, hydroxy-ethyl acrylate, propylene
Acid, methacrylic acid, acrylamide, any one or more in N hydroxymethyl acrylamide.
The preparation method of above-mentioned styrene-vinyl versatate acrylate class copolymer emulsion, wherein the step
In rapid 2, the dosage of emulsifier is the 2.0%~10% of polymerized monomer total amount by mass percentage；The emulsifier includes
Anion emulsifier, nonionic emulsifier, any one or more in reactive emulsifier.
The preparation method of above-mentioned styrene-vinyl versatate acrylate class copolymer emulsion, wherein the step
In rapid 2, the dosage of deionized water is the 10%~30% of pre-emulsion total amount by mass percentage.
The preparation method of above-mentioned styrene-vinyl versatate acrylate class copolymer emulsion, wherein the step
In rapid 3, by pre-emulsion at 80~100 DEG C, in the deionized water containing emulsifier using initiator carry out dropwise reaction 3~
7 hours.
The preparation method of above-mentioned styrene-vinyl versatate acrylate class copolymer emulsion, wherein described draws
Sending out agent is ammonium persulfate or other persulfates；The dosage of the initiator is copolymer emulsion total weight by mass percentage
0.3%~1.0%.
The preparation method of above-mentioned styrene-vinyl versatate acrylate class copolymer emulsion, wherein the step
In rapid 3, carrying out post-processing to resulting copolymer emulsion with oxidation-reduction method is at 65~70 DEG C, using tert-butyl hydroperoxide
Ordor removing is carried out to resulting copolymer emulsion with sodium formaldehyde sulfoxylate to handle 1 hour.
The preparation method of above-mentioned styrene-vinyl versatate acrylate class copolymer emulsion, wherein the step
In rapid 4, it is 2.0 that the pH value of copolymer emulsion, which is adjusted to pH value, with ammonium hydroxide or ammonium salt or other substances that can replace ammonium salt
~9.0.
The present invention also provides the styrene-vinyl versatate acrylate class prepared by above-mentioned method copolymerization
Lotion.
Styrene-vinyl versatate acrylate class copolymer emulsion provided by the invention and preparation method have following
Advantage:
Styrene-vinyl versatate acrylate class copolymer emulsion provided by the invention has the hardness of styrene-acrylic emulsion
Have tertiary acrylic emulsion toughness again, be a kind of adhesive force it is strong, just in soft synthetic emulsion, can be applied to high-grade coating and bonding
Agent has a extensive future.Also, the production method of styrene provided by the invention, tertiary ethylene carbonate, acrylate copolymer emulsion
Copolymer can be formed in water, have the characteristics that at low cost, feasibility is high, simple and easy, excellent effect.
Specific embodiment
A specific embodiment of the invention is further described below.
The preparation method of styrene-vinyl versatate acrylate class copolymer emulsion provided by the invention, this method packet
Contain: step 1, weighing each raw material in proportion；Including polymerized monomer, emulsifier, initiator etc.；Step 2, styrene polymerization list is taken
Body, tertiary ethylene carbonate polymerized monomer, esters of acrylic acid polymerization monomer are added in pre-emulsification kettle, add emulsifier and deionization
Water carries out pre-emulsification in deionized water under the action of emulsifier, obtains pre-emulsion；Step 3, by the resulting pre- cream of step 2
Liquid is under conditions of heating and thermal insulation, in the deionized water containing emulsifier, i.e., is dripped in original solution using initiator
Add, resulting copolymer emulsion is post-processed with oxidation-reduction method after reaction；Step 4, by the resulting copolymer emulsion tune of step 3
PH value is saved, removing residual monomer is then vacuumized, it is total that styrene-vinyl versatate acrylate class is obtained after filtering
Poly- lotion.
Preferably, the styrene polymerization monomer in step 2, tertiary ethylene carbonate polymerized monomer, esters of acrylic acid polymerization are single
The weight ratio of body is 100:(15~35): (4~10).
It includes butyl acrylate, butyl methacrylate, hydroxypropyl acrylate, acrylic acid hydroxyl that esters of acrylic acid, which polymerize monomer,
Ethyl ester, acrylic acid, methacrylic acid, acrylamide, any one or more in N hydroxymethyl acrylamide.
In step 2, the dosage of emulsifier is the 2.0%~10% of polymerized monomer total amount by mass percentage.Emulsifier
Include any one or more in anion emulsifier, nonionic emulsifier, reactive emulsifier.
Anion emulsifier is preferably emulsifier os (alkyl phenol ether sulfosuccinate sodium), A-103 (alkyl phenol polyether sulphur
Base amber acid monoester sodium salt), K12 (lauryl sodium sulfate), neopelex, nonylphenol polyoxyethylene ether ammonium sulfate,
Fatty alcohol polyoxyethylene ether sodium sulfosuccinate, fatty alcohol polyoxyethylene ether succinic acid sodium sulphate etc..Nonionic emulsifier is preferred
For NP-10 (nonylphenol polyoxyethylene ether -10), (alkylol is poly- by EFS-470 (alkylol polyether-type nonionic emulsifier), A-980
Ether type nonionic emulsifier) etc..Reactive emulsifier is preferably A-2405 (acrylamido sodium isopropyl xanthate), SVS (ethylene
Base sodium sulfonate), NRS-1025 (the extraordinary ether alcohol sulfate containing allyl), SR-10 (the environment-friendly type reactivity table of no nonyl phenyl
Face activating agent).
In step 2, the dosage of deionized water is the 10%~30% of pre-emulsion total amount by mass percentage.
In step 3, by pre-emulsion under the conditions of 80~100 DEG C, initiator is used in the deionized water containing emulsifier
It carries out dropwise reaction 3~7 hours.
Initiator is ammonium persulfate or other persulfates；The dosage of initiator is that copolymer emulsion is total by mass percentage
The 0.3%~1.0% of weight.
In step 3, carrying out post-processing to resulting copolymer emulsion with oxidation-reduction method is at 65~70 DEG C, using tertiary fourth
Base hydrogen peroxide and sodium formaldehyde sulfoxylate carry out ordor removing to resulting copolymer emulsion and handle 1 hour.That is, by tert-butyl hydroperoxide and hanging white
Block, which is added in copolymer emulsion, to react 1 hour.Tert-butyl hydroperoxide and the dosage of sodium formaldehyde sulfoxylate are well known by persons skilled in the art
Conventional amount used.Sodium formaldehyde sulfoxylate is also known as rongalite, is restored with formalin combination sodium hydrogensulfite obtained, and chemical name is sulphoxylic acid
Hydrogen sodium formaldehyde or sodium formaldehyde sulphoxylate, when room temperature, are relatively stable, have extremely strong reproducibility under high temperature, there is blanching effect.
The last handling process also can be omitted.
In step 4, with ammonium hydroxide or ammonium salt or other can replace pH value tune of the substance by copolymer emulsion of ammonium salt
It is 2.0~9.0 to pH value.
The present invention also provides the styrene-vinyl versatate acrylate class copolymer emulsions prepared by this method.
Below with reference to embodiment to styrene-vinyl versatate acrylate class copolymer emulsion provided by the invention and
Preparation method is further described.
Embodiment 1
A kind of preparation method of styrene-vinyl versatate acrylate class copolymer emulsion, it includes:
Step 1, each raw material is weighed in proportion；Including polymerized monomer, emulsifier, initiator etc..
Step 2, styrene polymerization monomer, tertiary ethylene carbonate polymerized monomer, esters of acrylic acid polymerization monomer is taken to be added pre-
In emulsifying kettle, emulsifier and deionized water are added, carries out pre-emulsification in deionized water under the action of emulsifier, is obtained pre-
Lotion.
Styrene polymerization monomer, tertiary ethylene carbonate polymerized monomer, the weight ratio of esters of acrylic acid polymerization monomer are 100:
15:4.
It includes butyl acrylate or butyl methacrylate that esters of acrylic acid, which polymerize monomer,.
The dosage of emulsifier is the 2.0% of polymerized monomer total amount by mass percentage.Emulsifier includes anionic emulsifying
Agent, nonionic emulsifier, any one or more in reactive emulsifier.
Anion emulsifier is preferably emulsifier os (alkyl phenol ether sulfosuccinate sodium).Nonionic emulsifier is preferably
NP-10 (nonylphenol polyoxyethylene ether -10).Reactive emulsifier is preferably A-2405 (acrylamido sodium isopropyl xanthate).
The dosage of deionized water is the 10% of pre-emulsion total amount by mass percentage.
Step 3, by the resulting pre-emulsion of step 2 under conditions of heating and thermal insulation, it is preferable that at 80~100 DEG C in containing
In the deionized water of emulsifier, i.e., it is added dropwise in original solution using initiator, with oxidation-reduction method to gained after reaction
Copolymer emulsion post-processed.
Initiator is ammonium persulfate or other persulfates；The dosage of initiator is that copolymer emulsion is total by mass percentage
The 0.3% of weight.It carries out dropwise reaction 3~7 hours.
Carrying out post-processing to resulting copolymer emulsion with oxidation-reduction method is at 65~70 DEG C, using tert-butyl hydroperoxide
Hydrogen and sodium formaldehyde sulfoxylate carry out ordor removing to resulting copolymer emulsion and handle 1 hour.
Step 4, the resulting copolymer emulsion of step 3 is adjusted into pH value, it is preferable that with ammonium hydroxide or ammonium salt or other can
To replace the substance of ammonium salt that the pH value of copolymer emulsion is adjusted to pH value as 2.0~9.0；Then removing residual monomer is vacuumized,
Styrene-vinyl versatate acrylate class copolymer emulsion is obtained after filtering.
The present embodiment additionally provides the styrene-vinyl versatate acrylate class copolymerization cream prepared by this method
Liquid.
Embodiment 2
A kind of preparation method of styrene-vinyl versatate acrylate class copolymer emulsion, it includes:
Step 1, each raw material is weighed in proportion；Including polymerized monomer, emulsifier, initiator etc..
Step 2, styrene polymerization monomer, tertiary ethylene carbonate polymerized monomer, esters of acrylic acid polymerization monomer is taken to be added pre-
In emulsifying kettle, emulsifier and deionized water are added, carries out pre-emulsification in deionized water under the action of emulsifier, is obtained pre-
Lotion.
Styrene polymerization monomer, tertiary ethylene carbonate polymerized monomer, the weight ratio of esters of acrylic acid polymerization monomer are 100:
20:6.
It includes hydroxypropyl acrylate and hydroxy-ethyl acrylate that esters of acrylic acid, which polymerize monomer,.
The dosage of emulsifier is the 4% of polymerized monomer total amount by mass percentage.Emulsifier include anion emulsifier,
Any one or more in nonionic emulsifier, reactive emulsifier.
Anion emulsifier is preferably A-103 (alkyl phenol polyether sulfo group amber acid monoester sodium salt) or K12 (dodecyl sulphate
Sodium).Nonionic emulsifier is preferably EFS-470 (alkylol polyether-type nonionic emulsifier).Reactive emulsifier is preferably SVS
(sodium vinyl sulfonate).
The dosage of deionized water is the 15% of pre-emulsion total amount by mass percentage.
Step 3, by the resulting pre-emulsion of step 2 under conditions of heating and thermal insulation, it is preferable that at 80~100 DEG C in containing
In the deionized water of emulsifier, i.e., it is added dropwise in original solution using initiator, with oxidation-reduction method to gained after reaction
Copolymer emulsion post-processed.
Initiator is ammonium persulfate or other persulfates；The dosage of initiator is that copolymer emulsion is total by mass percentage
The 0.5% of weight.It carries out dropwise reaction 3~7 hours.
Carrying out post-processing to resulting copolymer emulsion with oxidation-reduction method is at 65~70 DEG C, using tert-butyl hydroperoxide
Hydrogen and sodium formaldehyde sulfoxylate carry out ordor removing to resulting copolymer emulsion and handle 1 hour.
Step 4, the resulting copolymer emulsion of step 3 is adjusted into pH value, it is preferable that with ammonium hydroxide or ammonium salt or other can
To replace the substance of ammonium salt that the pH value of copolymer emulsion is adjusted to pH value as 2.0~9.0；Then removing residual monomer is vacuumized,
Styrene-vinyl versatate acrylate class copolymer emulsion is obtained after filtering.
The present embodiment additionally provides the styrene-vinyl versatate acrylate class copolymerization cream prepared by this method
Liquid.
Embodiment 3
A kind of preparation method of styrene-vinyl versatate acrylate class copolymer emulsion, it includes:
Step 1, each raw material is weighed in proportion；Including polymerized monomer, emulsifier, initiator etc..
Step 2, styrene polymerization monomer, tertiary ethylene carbonate polymerized monomer, esters of acrylic acid polymerization monomer is taken to be added pre-
In emulsifying kettle, emulsifier and deionized water are added, carries out pre-emulsification in deionized water under the action of emulsifier, is obtained pre-
Lotion.
Styrene polymerization monomer, tertiary ethylene carbonate polymerized monomer, the weight ratio of esters of acrylic acid polymerization monomer are 100:
25:7.
It includes acrylic or methacrylic acid that esters of acrylic acid, which polymerize monomer,.
The dosage of emulsifier is the 6% of polymerized monomer total amount by mass percentage.Emulsifier include anion emulsifier,
Any one or more in nonionic emulsifier, reactive emulsifier.
Anion emulsifier is preferably neopelex.Nonionic emulsifier is preferably A-980 (alkylol polyethers
Type nonionic emulsifier).Reactive emulsifier is preferably NRS-1025 (the extraordinary ether alcohol sulfate containing allyl).
The dosage of deionized water is the 20% of pre-emulsion total amount by mass percentage.
Step 3, by the resulting pre-emulsion of step 2 under conditions of heating and thermal insulation, it is preferable that at 80~100 DEG C in containing
In the deionized water of emulsifier, i.e., it is added dropwise in original solution using initiator, with oxidation-reduction method to gained after reaction
Copolymer emulsion post-processed.
Initiator is ammonium persulfate or other persulfates；The dosage of initiator is that copolymer emulsion is total by mass percentage
The 0.65% of weight.It carries out dropwise reaction 3~7 hours.
Carrying out post-processing to resulting copolymer emulsion with oxidation-reduction method is at 65~70 DEG C, using tert-butyl hydroperoxide
Hydrogen and sodium formaldehyde sulfoxylate carry out ordor removing to resulting copolymer emulsion and handle 1 hour.
Step 4, the resulting copolymer emulsion of step 3 is adjusted into pH value, it is preferable that with ammonium hydroxide or ammonium salt or other can
To replace the substance of ammonium salt that the pH value of copolymer emulsion is adjusted to pH value as 2.0~9.0；Then removing residual monomer is vacuumized,
Styrene-vinyl versatate acrylate class copolymer emulsion is obtained after filtering.
The present embodiment additionally provides the styrene-vinyl versatate acrylate class copolymerization cream prepared by this method
Liquid.
Embodiment 4
A kind of preparation method of styrene-vinyl versatate acrylate class copolymer emulsion, it includes:
Step 1, each raw material is weighed in proportion；Including polymerized monomer, emulsifier, initiator etc..
Step 2, styrene polymerization monomer, tertiary ethylene carbonate polymerized monomer, esters of acrylic acid polymerization monomer is taken to be added pre-
In emulsifying kettle, emulsifier and deionized water are added, carries out pre-emulsification in deionized water under the action of emulsifier, is obtained pre-
Lotion.
Styrene polymerization monomer, tertiary ethylene carbonate polymerized monomer, the weight ratio of esters of acrylic acid polymerization monomer are 100:
30:9.
It includes acrylamide, N hydroxymethyl acrylamide that esters of acrylic acid, which polymerize monomer,.
The dosage of emulsifier is the 8% of polymerized monomer total amount by mass percentage.Emulsifier include anion emulsifier,
Any one or more in nonionic emulsifier, reactive emulsifier.Anion emulsifier is preferably Nonyl pheno
Ether ammonium sulfate.Nonionic emulsifier is preferably that (alkylol polyether-type is non-by NP-10 (nonylphenol polyoxyethylene ether -10) or EFS-470
Ionic emulsifying agent).Reactive emulsifier is preferably SR-10 (the environment-friendly type reactive surfactant of no nonyl phenyl).
The dosage of deionized water is the 25% of pre-emulsion total amount by mass percentage.
Step 3, by the resulting pre-emulsion of step 2 under conditions of heating and thermal insulation, it is preferable that at 80~100 DEG C in containing
In the deionized water of emulsifier, i.e., it is added dropwise in original solution using initiator, with oxidation-reduction method to gained after reaction
Copolymer emulsion post-processed.
Initiator is ammonium persulfate or other persulfates；The dosage of initiator is that copolymer emulsion is total by mass percentage
The 0.8% of weight.It carries out dropwise reaction 3~7 hours.
Carrying out post-processing to resulting copolymer emulsion with oxidation-reduction method is at 65~70 DEG C, using tert-butyl hydroperoxide
Hydrogen and sodium formaldehyde sulfoxylate carry out ordor removing to resulting copolymer emulsion and handle 1 hour.
Step 4, the resulting copolymer emulsion of step 3 is adjusted into pH value, it is preferable that with ammonium hydroxide or ammonium salt or other can
To replace the substance of ammonium salt that the pH value of copolymer emulsion is adjusted to pH value as 2.0~9.0；Then removing residual monomer is vacuumized,
Styrene-vinyl versatate acrylate class copolymer emulsion is obtained after filtering.
The present embodiment additionally provides the styrene-vinyl versatate acrylate class copolymerization cream prepared by this method
Liquid.
Embodiment 5
A kind of preparation method of styrene-vinyl versatate acrylate class copolymer emulsion, it includes:
Step 1, each raw material is weighed in proportion；Including polymerized monomer, emulsifier, initiator etc..
Step 2, styrene polymerization monomer, tertiary ethylene carbonate polymerized monomer, esters of acrylic acid polymerization monomer is taken to be added pre-
In emulsifying kettle, emulsifier and deionized water are added, carries out pre-emulsification in deionized water under the action of emulsifier, is obtained pre-
Lotion.
Styrene polymerization monomer, tertiary ethylene carbonate polymerized monomer, the weight ratio of esters of acrylic acid polymerization monomer are 100:
35:10.
It includes butyl acrylate, butyl methacrylate, hydroxypropyl acrylate, acrylic acid hydroxyl that esters of acrylic acid, which polymerize monomer,
Ethyl ester, acrylic acid, methacrylic acid, acrylamide, any one or more in N hydroxymethyl acrylamide.
The dosage of emulsifier is the 10% of polymerized monomer total amount by mass percentage.Emulsifier includes anionic emulsifying
Agent, nonionic emulsifier, any one or more in reactive emulsifier.
Anion emulsifier is preferably fatty alcohol polyoxyethylene ether sodium sulfosuccinate and fatty alcohol polyoxyethylene ether amber
Sour sodium sulphate etc..Nonionic emulsifier is preferably EFS-470 (alkylol polyether-type nonionic emulsifier) or A-980 (alkylol
Polyether-type nonionic emulsifier).Reactive emulsifier is preferably A-2405 (acrylamido sodium isopropyl xanthate) or SVS (second
Sodium olefin sulfonate).
The dosage of deionized water is the 30% of pre-emulsion total amount by mass percentage.
Step 3, by the resulting pre-emulsion of step 2 under conditions of heating and thermal insulation, it is preferable that at 80~100 DEG C in containing
In the deionized water of emulsifier, i.e., it is added dropwise in original solution using initiator, with oxidation-reduction method to gained after reaction
Copolymer emulsion post-processed.
Initiator is ammonium persulfate or other persulfates；The dosage of initiator is that copolymer emulsion is total by mass percentage
The 1.0% of weight.It carries out dropwise reaction 3~7 hours.
Carrying out post-processing to resulting copolymer emulsion with oxidation-reduction method is at 65~70 DEG C, using tert-butyl hydroperoxide
Hydrogen and sodium formaldehyde sulfoxylate carry out ordor removing to resulting copolymer emulsion and handle 1 hour.
Step 4, the resulting copolymer emulsion of step 3 is adjusted into pH value, it is preferable that with ammonium hydroxide or ammonium salt or other can
To replace the substance of ammonium salt that the pH value of copolymer emulsion is adjusted to pH value as 2.0~9.0；Then removing residual monomer is vacuumized,
Styrene-vinyl versatate acrylate class copolymer emulsion is obtained after filtering.
The present embodiment additionally provides the styrene-vinyl versatate acrylate class copolymerization cream prepared by this method
Liquid.
Styrene-vinyl versatate acrylate class copolymer emulsion provided by the invention and preparation method, can be in water
Middle formation copolymer, water therein use deionized water, styrene, tertiary ethylene carbonate, the acrylic ester copolymerization cream of acquisition
There is liquid the hardness of styrene-acrylic emulsion to have tertiary acrylic emulsion toughness again, be a kind of adhesive force it is strong, just in soft synthetic emulsion, Neng Gouying
For high-grade coating and adhesive, have a extensive future.The preparation method also has that at low cost, feasibility is high, simple and easy, effect is excellent
The features such as different.
It is discussed in detail although the contents of the present invention have passed through above preferred embodiment, but it should be appreciated that above-mentioned
Description is not considered as limitation of the present invention.After those skilled in the art have read above content, for of the invention
A variety of modifications and substitutions all will be apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (10)
1. a kind of preparation method of styrene-vinyl versatate acrylate class copolymer emulsion, which is characterized in that described
Method includes:
Step 1, each raw material is weighed in proportion；
Step 2, take styrene polymerization monomer, tertiary ethylene carbonate polymerized monomer, esters of acrylic acid polymerization monomer that pre-emulsification is added
In kettle, emulsifier is added, carries out pre-emulsification in deionized water, obtains pre-emulsion；
Step 3, the resulting pre-emulsion of step 2 is added dropwise using initiator under conditions of heating and thermal insulation, oxygen is used after reaction
Change reduction method to post-process resulting copolymer emulsion；
Step 4, the resulting copolymer emulsion of step 3 is adjusted into pH value, then vacuumizes removing residual monomer, obtained after filtering
Styrene-vinyl versatate acrylate class copolymer emulsion.
2. the preparation method of styrene-vinyl versatate acrylate class copolymer emulsion as described in claim 1, special
Sign is that the styrene polymerization monomer, tertiary ethylene carbonate polymerized monomer, esters of acrylic acid in the step 2 polymerize monomer
Weight ratio be 100:(15~35): (4~10).
3. the preparation method of styrene-vinyl versatate acrylate class copolymer emulsion as claimed in claim 2, special
Sign is that the esters of acrylic acid polymerization monomer includes butyl acrylate, butyl methacrylate, hydroxypropyl acrylate, third
Olefin(e) acid hydroxyl ethyl ester, acrylic acid, methacrylic acid, acrylamide, any one or more in N hydroxymethyl acrylamide.
4. the preparation method of styrene-vinyl versatate acrylate class copolymer emulsion as described in claim 1, special
Sign is, in the step 2, the dosage of emulsifier is the 2.0%~10% of polymerized monomer total amount by mass percentage；Institute
The emulsifier stated includes any one or more in anion emulsifier, nonionic emulsifier, reactive emulsifier.
5. the preparation method of styrene-vinyl versatate acrylate class copolymer emulsion as described in claim 1, special
Sign is, in the step 2, the dosage of deionized water is the 10%~30% of pre-emulsion total amount by mass percentage.
6. the preparation method of styrene-vinyl versatate acrylate class copolymer emulsion as described in claim 1, special
Sign is, in the step 3, by pre-emulsion at 80~100 DEG C, is carried out dropwise reaction 3~7 hours using initiator.
7. the preparation method of styrene-vinyl versatate acrylate class copolymer emulsion as claimed in claim 6, special
Sign is that the initiator is ammonium persulfate or persulfate；The dosage of the initiator is altogether by mass percentage
The 0.3%~1.0% of poly- lotion total weight.
8. the preparation method of styrene-vinyl versatate acrylate class copolymer emulsion as described in claim 1, special
Sign is, in the step 3, carrying out post-processing to resulting copolymer emulsion with oxidation-reduction method is adopted at 65~70 DEG C
Ordor removing is carried out to resulting copolymer emulsion with tert-butyl hydroperoxide and sodium formaldehyde sulfoxylate to handle 1 hour.
9. the preparation method of styrene-vinyl versatate acrylate class copolymer emulsion as described in claim 1, special
Sign is, in the step 4, it is 2.0~9.0 that the pH value of copolymer emulsion, which is adjusted to pH value, with ammonium hydroxide or ammonium salt.
10. a kind of styrene-tertiary ethylene carbonate-the third prepared by the method by as described in any one of claim 1~9
Olefin(e) acid esters copolymer emulsion.
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| CN111848851A (en) * | 2020-06-18 | 2020-10-30 | 南京工业大学 | Preparation method of ethylene-tert-carbonate-modified monodisperse colloid emulsion |
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| CN103626915A (en) * | 2013-12-16 | 2014-03-12 | 烟台前进化工有限公司 | Production method of special adhesive for cement shuttering |
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| CN103626915A (en) * | 2013-12-16 | 2014-03-12 | 烟台前进化工有限公司 | Production method of special adhesive for cement shuttering |
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| CN111848851A (en) * | 2020-06-18 | 2020-10-30 | 南京工业大学 | Preparation method of ethylene-tert-carbonate-modified monodisperse colloid emulsion |
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