CN109575176A - A kind of preparation method of crosslinkable vinyl chloride polymer - Google Patents
A kind of preparation method of crosslinkable vinyl chloride polymer Download PDFInfo
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- CN109575176A CN109575176A CN201811404324.6A CN201811404324A CN109575176A CN 109575176 A CN109575176 A CN 109575176A CN 201811404324 A CN201811404324 A CN 201811404324A CN 109575176 A CN109575176 A CN 109575176A
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- C—CHEMISTRY; METALLURGY
- 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
- C08F214/00—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 a halogen
- C08F214/02—Monomers containing chlorine
- C08F214/04—Monomers containing two carbon atoms
- C08F214/06—Vinyl chloride
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- C—CHEMISTRY; METALLURGY
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
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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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
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- C—CHEMISTRY; METALLURGY
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- 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
- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
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Abstract
The invention discloses a kind of preparation methods of crosslinkable vinyl chloride polymer, are related to chemical industry macromolecule synthesising technology field, this method comprises the following steps: the function monomer with plasticising function being dissolved in crosslinking agent to prepare and be crosslinked function monomer solution first；Then dispersant solution and crosslinking function monomer solution, initiator are stirred evenly together cross-linked disperse liquid is made；Then vinyl chloride monomer, crosslinking function monomer solution, other auxiliary agents and cross-linked disperse liquid are added in polymeric kettle and carry out polymerization reaction, being eventually adding terminator, reaction was completed, can be prepared by crosslinkable vinyl chloride polymer.Strong operability of the present invention, technical process are easy to control, and vinyl chloride polymer products crosslinking produced by the present invention and plasticizing effect are significant, have excellent processing melt flowability and plasticizing capacity, " flake " is few after product is processed, appearance and excellent in mechanical performance.
Description
Technical field
The present invention relates to chemical industry macromolecule synthesising technology field, especially a kind of preparation side of crosslinkable vinyl chloride polymer
Method.
Background technique
Polyvinyl chloride is because it has relatively excellent comprehensive mechanical property, anti-flammability and chemical resistance etc., in reality
It is widely used；But the drawbacks such as that there is also brittleness is big for it, erosion-resisting characteristics is poor, to seriously constrain it in certain specific areas
Development.Currently, resin generation table can be made by introducing filling cross-linked modifier in Corvic process
Face deformation, enhances product performance, and then increases the application field of Corvic, but at the same time, fills cross-linked modifier
Introducing the problems such as may bringing surface deterioration or undesirable mechanical property to resin again.
Specifically, this change for preparing Corvic with introducing filling cross-linked modifier generallyd use now
Synthetic method is learned, refers to that crosslinking agent is added during chloroethylene polymerization participates in polymerization reaction together, and the crosslinking agent is general
With two or more reactive functional structures, and require its can with chloroethylene copolymer and make polyvinyl chloride strand send out
First portion crosslinking.In addition, the mode that the addition of crosslinking agent generallys use in the prior art is added at one time before polymerization starts,
Or be added in batches in polymerization process or continuous be added dropwise is added, delustring crosslinked resin is synthesized with this technique.
Using crosslinked resin made from this method, due to the presence of micro- cross-linked structure on polyvinyl chloride strand, resin exists
Under melting temperature when machine-shaping, when being changed into viscous state by elastomeric state, under strong shear action, macromolecular is solved
It twines and slides, generate deformation；With the reduction of temperature after molding, there are a relaxation, different microstructures for material
Contraction in relaxation is different, causes the difference of product internal structure, and product surface is made to have certain permanent deformation
Performance.In addition, its resistance to heat distorsion, solvent resistance, resistance to ag(e)ing can be improved after polyvinyl chloride strand is crosslinked, change
Its physical mechanical property and electric property, therefore the type crosslinked resin is widely used in insulated cable, electric wire, matt film, door
The fields such as window sealing strip, instrument board.
For example, patent publication No. is Chinese patent " the synthesis side of special resin for dulling polyvinyl chloride of CN1634999A
Method ", the synthetic method are in conventional suspension polymerization of VC reaction system, and crosslinking agent is when polymerisation conversion is 20~35%
A kind of crosslinking agent is added when being used in combination in disposable all additions or crosslinking agent before the beginning of the polymerization, in polymerization reaction
Another crosslinking agent is added in conversion ratio when reaching 30~40%, the dulling polyvinyl chloride proper tree of certain gel content can be made
Rouge.
Similar publication is there are also very much, using the method for the type only in conventional suspension polymerization of VC reactant
In system, relatively simple introducing delustring crosslinking agent, although delustring crosslinked resin obtained can obtain relatively in some aspects
Good performance, but it but exists be not easy to be plasticized or be plasticized non-uniform situation in process, product after processing is " brilliant
Point " and " flake " are more, and the appearance and physical and mechanical property of product are poor.
Summary of the invention
In order to overcome the above-mentioned deficiencies of the prior art, the present invention provides a kind of preparation sides of crosslinkable vinyl chloride polymer
Method, by this method can be made short texture, " flake " less, be easy to be plasticized and high specific surface area crosslinkable vinyl chloride polymerize
Object.
The technical scheme adopted by the invention is that:
A kind of preparation method of crosslinkable vinyl chloride polymer, includes the following steps:
(a) it is crosslinked the preparation of function monomer solution
To there is the function monomer of plasticising function to be dissolved in crosslinking agent, obtain crosslinking function monomer solution, then will
It is divided into crosslinking function monomer solution A and crosslinking function monomer solution B two parts are spare；
(b) preparation of cross-linked disperse liquid
Take dispersing agent to be configured to solution, after stirred evenly together with crosslinking function monomer solution A, initiator again, obtain
Cross-linked disperse liquid, cross-linked disperse liquid need logical cooling water to carry out cold insulation；
(c) suspension polymerization of VC prepares crosslinkable vinyl chloride polymer
After polymeric kettle coats anti-fouling agent and rinses well first, by pure water, vinyl chloride monomer, pH adjusting agent, crosslinking function
Energy monomer solution B, dispersing agent and initiator are separately added into polymeric kettle, and control reaction temperature is 30~72 DEG C, polymerization process
Start water filling and timing after starting；Then after polymerization reaction starts 15~180min again at the uniform velocity be continuously added to cross-linked disperse
Liquid；After last reaction system pressure to be polymerized drops to 0.03~0.15MPa of process set value, terminator is added, and reaction was completed, instead
It answers product to carry out centrifugal drying after stripping, can be prepared by crosslinkable vinyl chloride polymer.
It is not easy to be plasticized or be plasticized it has been recognised by the inventors why crosslinked resin made from the prior art exists in process
Non-uniform situation, and product " crystal point ", " flake " are more after processing, main reason is that, the introducing meeting of crosslinking agent first
Make inside crosslinked pvc resin that there are cross-linked structures, and in the prior art, it is previous that reaction is usually taken in the addition of crosslinking agent
Secondary property such as is added, is added or is continuously added in batches during the reaction at the relatively simple adding manner, so as to cause obtained
Chemical crosslinking resin inner gel and sol ingredient are unevenly distributed, the crosslinking degree of gel is unequal.Therefore, how to make crosslinked resin
Inner gel and sol ingredient distribution, gel cross-linkage degree presentation uniformity are the technical problem to be solved in the present invention.
In the present invention, in order to realize the purpose of above-mentioned " uniformity ", no longer using in suspension polymerization of VC reaction system
In simple introducing crosslinked agent way, but will have the function monomer of plasticising function be dissolved in crosslinking agent first and prepare crosslinking
Then function monomer solution takes partial cross-linked function monomer solution to be uniformly mixed with dispersant solution, initiator and crosslinking point is made
Dispersion liquid finally again hangs crosslinking function monomer solution and cross-linked disperse liquid under a series of other auxiliary agent collaborations with vinyl chloride
Floating polymerization reaction, to prepare crosslinkable vinyl chloride polymer.As can be seen that in order to solve the technical problem, the present invention not only introduces friendship
The mode for joining agent is different, and also introduces the function monomer with plasticising function and participate in polymerization reaction together.
In step (a), on the one hand, introduce the function monomer with plasticising function in crosslinked resin preparation process, allow it
It is copolymerized with vinyl chloride, that is, the preferable low temperature toughening group of compatibility is introduced on polyvinyl chloride skeleton,
It is demonstrated experimentally that this measure can improve polyvinyl chloride macromolecular chain structure, the plasticizing capacity of final polymerizate is greatly promoted；It is another
The function monomer for having plasticising function is dissolved in preparation crosslinking function monomer solution in crosslinking agent, can realize elder generation by aspect
So that the two is sufficiently mixed, mutually wrapped up, first allows function monomer and crosslinking agent with plasticising function that grafting adequately occurs poly-
Reaction is closed, to form chemical bonding structure；What needs to be explained here is that having function monomer, crosslinking agent, the chlorine of plasticising function
The reactivity ratio of ethylene three is variant, and in same polymerization system, the mutual copolymerization rates of three, extent of reaction etc. are all
Difference is had, and there is function monomer, the crosslinking agent of plasticising function compared to the additional amount of vinyl chloride monomer in the present invention
Additional amount it is less, thus can obviously know that there is the function monomer of plasticising function, the addition time of crosslinking agent, be added
Amount, addition speed etc. can cause significant impact to the composition of final polymer；So the function list that will there is plasticising function first
Crosslinking function monomer solution is made in body and crosslinking agent hybrid reaction, not only subsequent step to crosslinking function monomer solution at
Reason is made cross-linked disperse liquid and provides raw material basis, and this crosslinking function monomer solution is participated in vinyl chloride below and suspended and is gathered
After closing reaction system, there is very big facilitation to the uniformity of component distribution and crosslinking degree in crosslinked resin product is promoted, from
And realize the purpose of soffening in enhancing crosslinked resin process.
As for step (b), partial cross-linked function monomer solution made from step (a) is further processed herein,
Dispersing agent adequately disperses that the fine drop of uniform particle sizes can be dispersed into, and due to initiator activity under package action
The presence of free radical may eventually form uniform active drop, i.e. cross-linked disperse liquid, and chloroethene is added in this uniform active drop
In alkene suspension polymerization system, and in the case where step (a) crosslinking function monomer solution obtained and the collaboration of other auxiliary agents participate in, activity
Uniformly with vinyl chloride graft copolymerization can occur for drop, to promote the uniformity of polymers compositions, realize crosslinking degree
Uniformity, and then promote the delustring cross-linking properties of product, while also having promotion to the processing melt flowability of polymerizate
Effect；Thus, finally crosslinked resin obtained can have excellent plasticizing capacity, the product after processing in process to the present invention
" flake " is few, and the appearance and excellent in mechanical performance of resin is made.
Further, in abovementioned steps by weight, total dosage of each raw material are as follows: 100 parts of vinyl chloride monomer, have and increase
0.001~10 part of function monomer for moulding function, 0.5~5 part of crosslinking agent, 110~150 parts of pure water, 0.06~0.15 part of dispersing agent,
0.03~0.06 part of initiator, 0.003~0.04 part of pH adjusting agent, polymerization process fills the water 20~50 parts, terminator 0.05
~0.1 part；Wherein, the dispersant dosage that cross-linked disperse liquid is prepared in step (b) is 0.003~0.01 part, and initiator amount is
0.005~0.04 part.
Preferably, the function monomer described in step (a) with plasticising function is butyl acrylate (BA), ethyl acrylate
(EA), one or more of Hexyl 2-propenoate (HA), acrylic acid-2-ethyl caproite (2-EHA) combine.
Preferably, crosslinking agent described in step (a) is allyl methacrylate, 1,4-butanediol diacrylate, neighbour
Dially phthalate, diallyl maleate, triallyl cyanurate, divinylbenzene, ethylene glycol dimethyl propylene
The combination of one or more of acid esters, glycerine two (methyl) acrylate, polyethyleneglycol diacrylate.
Preferably, it is the high alcoholysis degree polyvinyl alcohol (PVA) of 80~90mol%, alcoholysis degree that the dispersing agent, which is alcoholysis degree,
It is the middle alcoholysis degree polyvinyl alcohol of 70~80mol%, the polyvinyl alcohol of alcoholysis degree < 55mol%, methylcellulose (MC), hydroxyl second
The combination of one or more of base cellulose (HEC), hydroxypropyl methyl cellulose (HPMC).
Preferably, the initiator is dicetyl peroxydicarbonate two (2- ethyl hexyl) ester (EHP), peroxidating neodecanoic acid isopropylbenzene
Bis- (3,3,5- trimethyl) hexanoyls (TMHP) of ester (CNP), peroxidating, new peroxide tert-butyl caprate (BNP), azodiisobutyronitrile
(AIBN), one or more of azobisisoheptonitrile (ABVN) combines.
Preferably, pH adjusting agent described in step (c) is sodium bicarbonate (NaHCO3), ammonium hydrogen carbonate (NH4HCO3), ammonium hydroxide,
One of sodium hydroxide.
Preferably, terminator described in step (c) be α-methylstyrene, acetone semicarbazone thiocarbamide (ATSC), bisphenol-A,
The combination of one or more of N, N- diethyl hydroxylamine (DEHA).
Preferably, cooling water described in step (b) is normal temperature circulation cooling water, 5 DEG C of constant temp cooling waters, 7 DEG C of constant temperature coolings
One of water.
The beneficial effects of the present invention are: improving polymer group present invention improves the internal structure of Corvic
The uniformity divided improves the uniformity of crosslinking degree in resin, obtained vinyl chloride polymer products crosslinking and plasticizing effect
Fruit is significant, has excellent processing melt flowability and plasticizing capacity, and product processed rear " flake " is few, appearance and mechanics
It has excellent performance；The method of the present invention strong operability simultaneously, operating process is easy, steady, easy to control, and polymerization reaction is stablized, product
Difference between batch is small, is easy to industrial-scale production.
Specific embodiment
The present invention will be further described below in conjunction with the embodiments.
Embodiment 1
A kind of preparation method of crosslinkable vinyl chloride polymer, includes the following steps:
(a) it is crosslinked the preparation of function monomer solution
0.08 part of butyl acrylate is dissolved in 0.8 part of crosslinking agent polyethyleneglycol diacrylate, crosslinking function is obtained
Energy monomer solution is then classified as crosslinking function monomer solution A and crosslinking function monomer solution B two that weight ratio respectively accounts for 50%
Part is spare；
(b) preparation of cross-linked disperse liquid
The polyvinyl alcohol that 0.005 part of alcoholysis degree is 80mol% is taken to be configured to the solution that mass fraction is 3%, then by it
(initiator is by EHP and CNP group with all crosslinking function monomer solution A and 0.01 part of initiator obtained in step (a)
At wherein the mass ratio of EHP and CNP is 2.5:1) it stirs evenly together, obtain cross-linked disperse liquid, cross-linked disperse liquid configuration 5
DEG C constant temp cooling water carries out cold insulation；
(c) suspension polymerization of VC prepares self-plasticization type Corvic
After polymeric kettle coats anti-fouling agent and rinses well first, using whole enclosed charging and warm water fed technology is waited,
It is automatically added to 130 parts of isothermal pure water, 100 parts of vinyl chloride monomer, 0.01 part into polymeric kettle respectively by DCS process control
NH4HCO3And (dispersing agent is grouped as dispersing agent by the group of following parts by weight: 0.015 part of HPMC, 0.053 part of alcoholysis degree
PVA that PVA, 0.03 part of alcoholysis degree for 71.0~73.5mol% are 78.5~81.5mol%, 0.01 part of alcoholysis degree be 45~
The PVA of 51mol%), 0.035 part of initiator (initiator is made of EHP and CNP, and wherein EHP and CNP mass ratio are 2.5:
1), all crosslinking function monomer solution Bs obtained in step (a)；It is 57 DEG C that charging, which finishes i.e. control polymeric reaction temperature, poly-
Start water filling and timing after closing reaction starting, water injection rate is 35 parts, after polymerization reaction starts 30min, starts at the uniform velocity continuous
Whole cross-linked disperse liquid obtained in step (b) are added, add up to be added the time as 60min；Under stirring and cooling water effect, according to
So control polymerization temperature is at 57 DEG C, after polymerization system pressure is down to 0.1MPa, 0.08 part of terminator DEHA is added and terminates reaction,
Reaction product discharges after mixing evenly, then centrifugal drying is carried out after stripping, and can be prepared by crosslinkable vinyl chloride polymer.
Embodiment 2
A kind of preparation method of crosslinkable vinyl chloride polymer, includes the following steps:
(a) it is crosslinked the preparation of function monomer solution
0.05 part of butyl acrylate is dissolved in 0.9 part of crosslinking agent polyethyleneglycol diacrylate, crosslinking function is obtained
Energy monomer solution, is then classified as the crosslinking function monomer solution A that weight ratio is 40% and the crosslinking function that weight ratio is 60%
Energy monomer solution B two parts are spare；
(b) preparation of cross-linked disperse liquid
The polyvinyl alcohol that 0.005 part of alcoholysis degree is 80mol% is taken to be configured to the solution that mass fraction is 3%, then by it
(initiator is by EHP and CNP group with all crosslinking function monomer solution A and 0.01 part of initiator obtained in step (a)
At wherein the mass ratio of EHP and CNP is 2.5:1) it stirs evenly together, obtain cross-linked disperse liquid, cross-linked disperse liquid configuration 5
DEG C constant temp cooling water carries out cold insulation；
(c) suspension polymerization of VC prepares self-plasticization type Corvic
After polymeric kettle coats anti-fouling agent and rinses well first, using whole enclosed charging and warm water fed technology is waited,
It is automatically added to 135 parts of isothermal pure water, 100 parts of vinyl chloride monomer, 0.01 part into polymeric kettle respectively by DCS process control
NH4HCO3And (dispersing agent is grouped as by the group of following parts by weight: 0.04 part of HPMC, 0.08 part of alcoholysis degree are dispersing agent
PVA that the PVA of 71.0~73.5mol%, 0.02 part of alcoholysis degree are 78.5~81.5mol%, 0.01 part of alcoholysis degree be 45~
The PVA of 51mol%), 0.035 part of initiator (initiator is made of EHP and CNP, and wherein EHP and CNP mass ratio are 2.5:
1), all crosslinking function monomer solution Bs obtained in step (a)；It is 57 DEG C that charging, which finishes i.e. control polymeric reaction temperature, poly-
Start water filling and timing after closing reaction starting, water injection rate is 35 parts, after polymerization reaction starts 15min, starts at the uniform velocity continuous
Whole cross-linked disperse liquid obtained in step (b) are added, add up to be added the time as 60min；Under stirring and cooling water effect, according to
So control polymerization temperature is at 57 DEG C, after polymerization system pressure is down to 0.1MPa, 0.08 part of terminator DEHA is added and terminates reaction,
Reaction product discharges after mixing evenly, then centrifugal drying is carried out after stripping, and can be prepared by crosslinkable vinyl chloride polymer.
Embodiment 3
A kind of preparation method of crosslinkable vinyl chloride polymer, includes the following steps:
(a) it is crosslinked the preparation of function monomer solution
0.05 part of butyl acrylate is dissolved in 1.2 parts of crosslinking agent polyethyleneglycol diacrylates, crosslinking function is obtained
Energy monomer solution, is then classified as the crosslinking function monomer solution A that weight ratio is 30% and the crosslinking function that weight ratio is 70%
Energy monomer solution B two parts are spare；
(b) preparation of cross-linked disperse liquid
The polyvinyl alcohol that 0.005 part of alcoholysis degree is 80mol% is taken to be configured to the solution that mass fraction is 3%, then by it
(initiator is by EHP and CNP group with all crosslinking function monomer solution A and 0.01 part of initiator obtained in step (a)
At wherein the mass ratio of EHP and CNP is 2.5:1) it stirs evenly together, obtain cross-linked disperse liquid, cross-linked disperse liquid configuration 5
DEG C constant temp cooling water carries out cold insulation；
(c) suspension polymerization of VC prepares self-plasticization type Corvic
After polymeric kettle coats anti-fouling agent and rinses well first, using whole enclosed charging and warm water fed technology is waited,
It is automatically added to 130 parts of isothermal pure water, 100 parts of vinyl chloride monomer, 0.01 part into polymeric kettle respectively by DCS process control
NH4HCO3And dispersing agent (dispersing agent is grouped as by the group of following parts by weight: 0.09 part of alcoholysis degree is 71.0~
PVA that the PVA of 73.5mol%, 0.035 part of alcoholysis degree are 78.5~81.5mol%, 0.01 part of alcoholysis degree are 45~51mol%
PVA), 0.035 part of initiator (initiator is made of EHP and CNP, and wherein EHP and CNP mass ratio are 2.5:1), step
(a) all crosslinking function monomer solution Bs obtained in；It is 57 DEG C that charging, which finishes i.e. control polymeric reaction temperature, in polymerization reaction
Start water filling and timing after starting, water injection rate is 35 parts, after polymerization reaction starts 30min, starts continuous addition step at the uniform velocity
Suddenly whole cross-linked disperse liquid obtained in (b), adds up to be added the time as 30min；Under stirring and cooling water effect, still control
Polymerization temperature is at 57 DEG C, after polymerization system pressure is down to 0.1MPa, 0.08 part of terminator DEHA is added and terminates reaction, reaction produces
Object discharges after mixing evenly, then centrifugal drying is carried out after stripping, and can be prepared by crosslinkable vinyl chloride polymer.
Embodiment 4
A kind of preparation method of crosslinkable vinyl chloride polymer, includes the following steps:
(a) it is crosslinked the preparation of function monomer solution
0.05 part of acrylic acid-2-ethyl caproite (2-EHA) is dissolved in 1 part of crosslinking agent polyethyleneglycol diacrylate,
Crosslinking function monomer solution is obtained, crosslinking function monomer solution A and crosslinking function that weight ratio respectively accounts for 50% are then classified as
Energy monomer solution B two parts are spare；
(b) preparation of cross-linked disperse liquid
The polyvinyl alcohol that 0.005 part of alcoholysis degree is 80mol% is taken to be configured to the solution that mass fraction is 3%, then by it
(initiator is by EHP and CNP with all crosslinking function monomer solution A and 0.015 part of initiator obtained in step (a)
Composition, wherein the mass ratio of EHP and CNP is 2.3:1) it stirs evenly together, obtain cross-linked disperse liquid, the configuration of cross-linked disperse liquid
5 DEG C of constant temp cooling waters carry out cold insulation；
(c) suspension polymerization of VC prepares self-plasticization type Corvic
After polymeric kettle coats anti-fouling agent and rinses well first, using whole enclosed charging and warm water fed technology is waited,
It is automatically added to 130 parts of isothermal pure water, 100 parts of vinyl chloride monomer, 0.01 part into polymeric kettle respectively by DCS process control
NH4HCO3And dispersing agent (dispersing agent is grouped as by the group of following parts by weight: 0.09 part of alcoholysis degree is 71.0~
PVA that the PVA of 73.5mol%, 0.035 part of alcoholysis degree are 78.5~81.5mol%, 0.01 part of alcoholysis degree are 45~51mol%
PVA), 0.035 part of initiator (initiator is made of EHP and CNP, and wherein EHP and CNP mass ratio are 2.5:1), step
(a) all crosslinking function monomer solution Bs obtained in；It is 57 DEG C that charging, which finishes i.e. control polymeric reaction temperature, in polymerization reaction
Start water filling and timing after starting, water injection rate is 35 parts, after polymerization reaction starts 15min, starts continuous addition step at the uniform velocity
Suddenly whole cross-linked disperse liquid obtained in (b), adds up to be added the time as 30min；Under stirring and cooling water effect, still control
Polymerization temperature is at 57 DEG C, after polymerization system pressure is down to 0.1MPa, 0.08 part of terminator DEHA is added and terminates reaction, reaction produces
Object discharges after mixing evenly, then centrifugal drying is carried out after stripping, and can be prepared by crosslinkable vinyl chloride polymer.
Comparative example
A kind of preparation method of polyvinyl chloride resins for universal use, includes the following steps:
After polymeric kettle coats anti-fouling agent and rinses well first, using whole enclosed charging and warm water fed technology is waited,
It is automatically added to 130 parts of isothermal pure water, 100 parts of vinyl chloride monomer, 0.01 part into polymeric kettle respectively by DCS process control
NH4HCO3And (dispersing agent is grouped as by the group of following parts by weight: 0.01 part of HPMC, 0.05 part of alcoholysis degree are dispersing agent
PVA that the PVA of 71.0~73.5mol%, 0.03 part of alcoholysis degree are 78.5~81.5mol%, 0.01 part of alcoholysis degree be 45~
The PVA of 51mol%), 0.045 part of initiator (initiator is made of EHP and CNP, and wherein EHP and CNP mass ratio are 2.5:
1)；It is 57 DEG C that charging, which finishes i.e. control polymeric reaction temperature, starts to fill the water after polymerization reaction starting, and water injection rate is 35 parts,
Under stirring and cooling water effect, polymerization temperature is still controlled at 57 DEG C, after polymerization system pressure is down to 0.1MPa, is added 0.08
Part terminator DEHA terminates reaction, and reaction product discharges after mixing evenly, then centrifugal drying is carried out after stripping, and can be prepared by gathering
Vinyl chloride resins for universal use.
Corvic product, quality index and performance test results obtained by the various embodiments described above and comparative example
It is as shown in the table:
1 Corvic properties of product detection case of table
As can be seen from the above table, compared to resins for universal use made from comparative example, the present invention will be by that will have plasticising function
The lower function monomer of glass transition temperature, the crosslinking agent with crosslinking function and dispersing agent and initiator uniformly mix, and can have
Effect eliminates the active dispersant liquid drop that uniformly wraps up, in polymerization process in a manner of being continuously added dropwise obtained by chloroethene
The cross-linking effect that alkene polymer product embodies becomes apparent, and " flake " is less.
Claims (9)
1. a kind of preparation method of crosslinkable vinyl chloride polymer, it is characterized in that: including the following steps:
(a) it is crosslinked the preparation of function monomer solution
To there is the function monomer of plasticising function to be dissolved in crosslinking agent, crosslinking function monomer solution is obtained, then by its point
It is spare for crosslinking function monomer solution A and crosslinking function monomer solution B two parts；
(b) preparation of cross-linked disperse liquid
Take dispersing agent to be configured to solution, after stirred evenly together with crosslinking function monomer solution A, initiator again, obtain crosslinking
Dispersion liquid, cross-linked disperse liquid need logical cooling water to carry out cold insulation；
(c) suspension polymerization of VC prepares crosslinkable vinyl chloride polymer
After polymeric kettle coats anti-fouling agent and rinses well first, by pure water, vinyl chloride monomer, pH adjusting agent, crosslinking function list
Liquid solution B, dispersing agent and initiator are separately added into polymeric kettle, and control reaction temperature is 30~72 DEG C, polymerization process starting
After start water filling and timing；Then after polymerization reaction starts 15~180min again at the uniform velocity be continuously added to cross-linked disperse liquid；Most
After reaction system pressure to be polymerized drops to 0.03~0.15MPa of process set value afterwards, terminator is added, and reaction was completed, reaction product
Centrifugal drying is carried out after stripping, and can be prepared by crosslinkable vinyl chloride polymer.
2. a kind of preparation method of crosslinkable vinyl chloride polymer as described in claim 1, it is characterized in that: by weight, respectively
Total dosage of raw material are as follows: 100 parts of vinyl chloride monomer, there is 0.001~10 part of function monomer of plasticising function, crosslinking agent 0.5~5
Part, 110~150 parts of pure water, 0.06~0.15 part of dispersing agent, 0.03~0.06 part of initiator, pH adjusting agent 0.003~0.04
Part, polymerization process fills the water 20~50 parts, 0.05~0.1 part of terminator；Wherein, cross-linked disperse liquid is prepared in step (b)
Dispersant dosage is 0.003~0.01 part, and initiator amount is 0.005~0.04 part.
3. a kind of preparation method of crosslinkable vinyl chloride polymer as described in claim 1, it is characterized in that: described in step (a)
Function monomer with plasticising function is butyl acrylate (BA), ethyl acrylate (EA), Hexyl 2-propenoate (HA), acrylic acid-
The combination of one or more of 2- ethylhexyl (2-EHA).
4. a kind of preparation method of crosslinkable vinyl chloride polymer as described in claim 1, it is characterized in that: described in step (a)
Crosslinking agent is allyl methacrylate, 1,4 butanediol diacrylate, diallyl phthalate, Malaysia diene acid third
Ester, divinylbenzene, ethylene glycol dimethacrylate, glycerine two (methyl) acrylate, gathers at triallyl cyanurate
The combination of one or more of glycol diacrylate.
5. a kind of preparation method of crosslinkable vinyl chloride polymer as described in claim 1, it is characterized in that: the dispersing agent is alcohol
The high alcoholysis degree polyvinyl alcohol (PVA) of 80~90mol% of solution degree, 70~80mol% of alcoholysis degree middle alcoholysis degree polyvinyl alcohol, alcohol
Polyvinyl alcohol, methylcellulose (MC), the hydroxyethyl cellulose (HEC), hydroxypropyl methyl cellulose of solution degree < 55mol%
One or more of (HPMC) combination.
6. a kind of preparation method of crosslinkable vinyl chloride polymer as described in claim 1, it is characterized in that: the initiator was
Aoxidize two carbonic acid two (2- ethyl hexyl) esters (EHP), cumyl peroxyneodecanoate (CNP), bis- (the 3,3,5- front threes of peroxidating
Base) hexanoyl (TMHP), new peroxide tert-butyl caprate (BNP), azodiisobutyronitrile (AIBN), in azobisisoheptonitrile (ABVN)
One or more kinds of combinations.
7. a kind of preparation method of crosslinkable vinyl chloride polymer as described in claim 1, it is characterized in that: described in step (c)
PH adjusting agent is sodium bicarbonate (NaHCO3), ammonium hydrogen carbonate (NH4HCO3), ammonium hydroxide, one of sodium hydroxide.
8. a kind of preparation method of crosslinkable vinyl chloride polymer as described in claim 1, it is characterized in that: described in step (c)
Terminator is α-methylstyrene, acetone semicarbazone thiocarbamide (ATSC), bisphenol-A, N, one of N- diethyl hydroxylamine (DEHA)
Or two or more combinations.
9. a kind of preparation method of crosslinkable vinyl chloride polymer as described in claim 1, it is characterized in that: described in step (b)
Cooling water is one of normal temperature circulation cooling water, 5 DEG C of constant temp cooling waters, 7 DEG C of constant temp cooling waters.
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| CN116768533A (en) * | 2023-06-27 | 2023-09-19 | 长春市城建维护集团股份有限公司 | Asphalt cold-patch material and preparation method thereof |
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