CN105273119B - A kind of preparation method of high degree of polymerization of polyvinyl chloride resin - Google Patents
A kind of preparation method of high degree of polymerization of polyvinyl chloride resin Download PDFInfo
- Publication number
- CN105273119B CN105273119B CN201410257523.4A CN201410257523A CN105273119B CN 105273119 B CN105273119 B CN 105273119B CN 201410257523 A CN201410257523 A CN 201410257523A CN 105273119 B CN105273119 B CN 105273119B
- Authority
- CN
- China
- Prior art keywords
- polymerization
- degree
- chain extender
- polyvinyl alcohol
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
A kind of preparation method of high degree of polymerization of polyvinyl chloride resin, belongs to PVC polymerization technique technical fields.Characterized in that, preparation technology is, chain extender, surfactant, deionized water stirring are melted into chain extender emulsification system first, wherein surfactant is the polyvinyl alcohol that the degree of polymerization is between 200 ~ 500, alcoholysis degree is between 30% ~ 55%；After vacuumizing, 100 ~ 200 parts of deionized waters of addition, 0.005 ~ 1 part of initiation system, 0.005 ~ 1 part of dispersion, 0.005 ~ 2 part of PH conditioning agent, 0.001 ~ 1 part of chain extender emulsification system and 100 parts of VCM and comonomer, start polymerisation based on pure weight of material part.The present invention simplifies technological operation while solving now conventional high polymerization degree resin " flake " number more shortcoming, eliminates chain extender and is continuously added to, due to adding speed change or the unstable random effect brought, make product quality more stable.
Description
Technical field
A kind of preparation method of high degree of polymerization of polyvinyl chloride resin, belongs to PVC polymerization technique technical fields.
Background technology
Polychloroethylene with high polymerization degree（HPVC）Resin generally refers to PVC of the average degree of polymerization 1700 ~ 4000.With it is common
PVC is compared, and it has a variety of excellent performances, such as higher resilience, relatively low compression set, excellent resistance to thermal change
Shape performance, higher tensile strength and excellent wearability, tear resistance, weather-proof, oil resistant, heat-resisting, cold-resistant, ozone resistance
Deng, Article Stiffness Determination varies with temperature small, the extinction with elastomeric material, be adapted as rubber replacement be used for sealing material
Material, sole materials, heat-resistant hose, heat-resisting cold resistant cable material etc., domestic annual consumption is about 100,000 tons, be it is a kind of have it is wide
The material of application prospect.
The synthesis of HPVC resins is based on suspension method, and polymerization technique can be subdivided into low temperature process and chain extender process again.Low temperature process
The resin of synthesis is higher in long chainline type, regularity and crystallinity, and quality of item is reliable, but polymerize heat transfer difficulty under low temperature
Greatly, hot systems requirement is removed to device harsh, the production cycle is long, so it is very necessary to aid in addition chain extender at high temperature.Expand
Chain agent method adds the reactive monomer with double bond, such as diallyl phthalate in polymerization system（DAP）, maleic acid
Diallyl（DAM）, TAC（TAIC）, glycol dinitrate ester acrylate（EGDMA）, glycerine two（First
Base）Acrylate, polyethyleneglycol diacrylate etc., make PVC is intermolecular to form crosslinking or tangle, degree of polymerization increase.
Resin producer initiator when producing high polymerization degree resin in part prepares solvent and still uses toluene, causes to give birth to
The noxious material such as toluene, nitrile group and vinyl chloride residual in polyvinyl chloride resin is produced, and thermal stability is deteriorated；Chain extension system is used
Method is single, and most of producers do not make any processing to chain extender, in polymerization initial stage directly by the higher chain extender of purity with it
Its reagent and additive in polymerization is disposably added in polymerization system, and this simple production process is easy to operate, is used by most producers, but
This technique produces resin process and easily forms more " flake ", has a strong impact on products appearance.
The content of the invention
The technical problem to be solved in the present invention is：Overcome prior art produce high polymerization degree resin " flake " number it is more,
There is provided a kind of system of the few high degree of polymerization of polyvinyl chloride resin of simple to operate, product " flake " for the undesirable shortcoming of products appearance
Preparation Method.
The technical solution adopted for the present invention to solve the technical problems is：The preparation side of the high degree of polymerization of polyvinyl chloride resin
Method, it is characterised in that specifically preparation technology is：
1）Chain extender is emulsified：By chain extender, surfactant, deionized water stirring chemical conversion chain extender content be 0.1% ~
20%th, surface-active contents obtain chain extender emulsification system for 0.05% ~ 2.0% homogeneous latex emulsion, and wherein surfactant is poly-
It is right between 200 ~ 500, polyvinyl alcohol of the alcoholysis degree between 30% ~ 55%；
2）HPVC polymerize：Reactor is evacuated to after -0.09MPa, 100 ~ 200 parts of addition is gone based on pure weight of material part
Ionized water, 0.005 ~ 1 part of initiation system, 0.008 ~ 1 part of dispersion, 0.005 ~ 2 part of PH conditioning agents, 0.001 ~ 1 part of chain extender
Emulsification system and 100 parts of VCM and comonomer, while start chuck water-bath circulation, system temperature in control polymeric kettle
Degree, when reaching 20 ~ 60 DEG C of reaction temperature, reaction starts timing；When polymerization reaches process endpoint, adding terminator makes instead
It should stop；Stirring reclaims monomer after 2 ~ 10 minutes, then emptying discharging, centrifugation slurry, drying.
The present invention is first to chain extender on the basis of the chain extension method that high degree of polymerization of polyvinyl chloride resin production technology is generally used
Surface-active-treatment first is carried out with low polymerization degree, polyvinyl alcohol with low alcoholysis level, is configured to can be applied to suspension polymerization of VC
Emulsification system, the technique for being then disposably added to polymerization system with other reagent and additive in polymerization in polymerization initial stage carries out high polymerization degree
The synthesis of polyvinyl chloride resin.The present invention passes through the preparation to chain extender emulsifying agent so that chain extender is once added in the early stage can be complete
The effect of chain extender emulsification is played, the high polymerization degree resin processing characteristics obtained by polymerization is excellent, particularly " flake " number is few, make
Product outward appearance is better than general product, solves and now commonly uses that high polymerization degree resin " flake " number is more, products appearance is undesirable lacks
Point, while simplify technological operation, eliminates chain extender and is continuously added in technique due to adding speed change or unstable bringing
Random effect, make product quality more stable.
Comonomer can be esters of acrylic acid, methyl acrylic ester or the olefines copolymerization reacted with chloroethylene copolymer
Monomer.
It is preferred that, step 1）Described in chain extender emulsification system in chain extender content be 0.5% ~ 10%.
Surfactant is dispersion aids used in suspension polymerization of VC system.It is preferred that, step 1）Described table
Face activating agent be the degree of polymerization be 200 ~ 300, alcoholysis degree be 45% ~ 55% between polyvinyl alcohol.Surfactant can be by chain extension
The scattered cladding of agent is a large amount of droplets, when surfactant is that 200 ~ 300, alcoholysis degree is between 45% ~ 55% from the degree of polymerization
During polyvinyl alcohol, the droplet formed by itself surface tension and combine the outstanding of itself and dispersant and polymerized monomer formation
Intermiscibility between supernatant liquid drop, obtains optimal chain extender controlled release ability, so as to ensure polymerization process stabilization, favorable dispersibility, reduces
" flake " formation.
Described deionized water needs to meet polymerization technique requirement, in case influence polymerisation, typically requires polymerization water
Electrical conductivity is 1 ~ 5 μ S/cm.
Step 2）Described in chain extender emulsification system addition parts by weight added in terms of pure chain extender quality be calculated as 0.01 ~
0.5 part.
Step 2）Described in dispersion be polyvinyl alcohol and cellulose in mass ratio 1:（0.5~1）Mixing disperse
Agent, wherein polyvinyl alcohol be the degree of polymerization in polyvinyl alcohol of 1000 ~ 1600, alcoholysis degree between 70% ~ 90% and the degree of polymerization 300
Between ~ 400, polyvinyl alcohol of the alcoholysis degree between 40% ~ 50% in mass ratio 1：3~3：1 mixture；Cellulose takes for methyl
Dai Du be the methylcellulose and hydroxypropyl substitution value that 1.6 ~ 1.9, content is 27% ~ 32% be 0.1 ~ 0.31, content be 4.0% ~
12.0%th, methyl substitution is that the hydroxypropyl methyl cellulose that 1.0 ~ 2.0, content is 19% ~ 30% is 1 in mass ratio：5~5：1
Compound cellulose.
Dispersion is to influence the principal element of polyvinyl chloride resin particle characteristic, and polymerization system is added to certain proportion
In, the interfacial tension of on the one hand reduction VCM and water is act as, is conducive to point of VCM under stirring
Dissipate；While the polymerisation of liquid droplets formation of suspension, dispersant adsorption plays a protective role in droplet surface, prevents coalescence.In this hair
Bright middle chain extender forms chain extender emulsion droplet, in condensate first with coordinating dispersant identical surfactant emulsifies
It is dispersed in system, and by coordinate the above-mentioned surfactant of consumption and identical component of the dispersant in dispersion come
The compatibility between chain extender emulsion droplet and polymerisation of liquid droplets is adjusted, is mixed when controlling and touch between two kinds of drops with this
Probability, and then control the slow release effect of chain extender.Make the process stabilization of whole polymerisation, more easily solve and now commonly use height
The problem of degree of polymerization resin " flake " number is more.
Described initiation system be free radical type initiator close, can trigger vinyl chloride gather, such as organic peroxide and
Azo compound, can be used alone or be made into compound system and use.Can be with arbitrary proportion between various azo-initiators
It is compound, can be compound with arbitrary proportion between various peroxide type initiators, azo-initiator and peroxide type initiators
Between can also arbitrary proportion compound use.
Described PH conditioning agents are tricalcium phosphate, sodium acid carbonate, ammonium hydrogen carbonate or sodium hydroxide.PH conditioning agents can be offset
The a small amount of hydrogen chloride produced in polymerization process, can be held essentially constant pH value in polymerization system.
The chain extender is diene or polyenic monomer, can be micromolecular compound or oligomer, such as adjacent benzene two
Formic acid diallyl（DAP）, diallyl maleate（DAM）, TAC（TAIC）, divinylbenzene（DVB）、
Glycol dinitrate ester acrylate（EGDMA）, glycerine two（Methyl）Acrylate or polyethyleneglycol diacrylate.It is preferred that
, the chain extender is diallyl phthalate or divinylbenzene.
The terminator includes free radical type terminator, quinones, polyatomic phenol, arylamine class, nitro compound, nitrosylation
Compound, organic sulfur compound, inorganic compound, terminator addition account for the 0.001% ~ 0.05% of vinyl chloride total amount.Terminator is added
Into polymerization system polymerisation can be made to stop completely or drastically slow down, reach the suitable purpose of control extent of polymerization.
Compared with prior art, the preparation method of high degree of polymerization of polyvinyl chloride resin of the invention is had the advantage that
It is：The present invention relates to the high degree of polymerization of polyvinyl chloride resin of a kind of " flake " number less, with good appearance（PVC）Preparation side
Method, more particularly to a kind of method that chain extension method technique prepares PVC with high.Gained polyvinyl chloride resin product " flake " number less,
Outward appearance is better than general resin, can be widely applied to high-grade CABLE MATERIALS, encapsulant, heat-resistant hose, film of evaporating brine, sole and uses
In terms of material, geomembrane, compared with prior art, the PVC with high that the process polymerisation provided according to the present invention is obtained
" flake " number is few, products appearance is better than general product, solves and now commonly uses that high polymerization degree resin " flake " number is more, product
The undesirable shortcoming of outward appearance, is a kind of synthetic method of high-quality HPVC resins.
The present invention adjusts the size of chain extender emulsion droplet by the emulsifying effectiveness of just right regulation chain extender, and
Attempt occur compatible probability when controlling emulsion droplet to be met with polymerisation of liquid droplets, finally to control the slow release effect of emulsifying agent, from
And the chain extender after emulsification can disposably be added, and make converging operation technique simpler.The technique of the present invention is by property
The disposable randomness for adding, eliminating continuous charging control of material, product quality is more stablized, get the raw materials ready with product processing it is convenient,
Man-hour is saved, and then increases yield.Other variables reduce so as to more effectively autotelic regulation and control high polymerization degree polychlorostyrene second
The parameters such as the degree of polymerization of alkene.
Embodiment
With reference to specific embodiment, the present invention will be further described, and wherein embodiment 1 is most preferred embodiment.Embodiment
In involved number be parts by weight
Embodiment 1：
Chain extender emulsification system is first prepared, then carries out chloroethylene polymerization.
Process for preparation is as follows：
Chain extender emulsification system（Solid content 1.0%）：1 portion of chain extender diallyl phthalate is added to preformulation
Obtain in polyvinyl alcohol water solution, chain extension system obtains chain extender emulsification system without obvious lamination after stirring 60 minutes, wherein
Polyvinyl alcohol water solution is that 2 parts of degree of polymerization are that the polyvinyl alcohol of solid content 35% that 300, alcoholysis degree is 45% is added to 96 parts of deionizations
Water, which stirs, to be formed.
Dispersion：High alcoholysis degree polyvinyl alcohol by the degree of polymerization in 1200, alcoholysis degree 80%（Solid content 5%）/ polymerization
Degree is the polyvinyl alcohol with low alcoholysis level that 300, alcoholysis degree is 45%（Solid content 35%）/ methyl substitution is that 1.7, content is 30%
Methylcellulose/hydroxypropyl substitution value is that 0.18, content is that 8%, methyl substitution is the hydroxypropyl methyl that 1.5, content is 25%
Cellulose presses pure dispersant mass ratio 1.5：1：1：0.5 uniform mixing.
Polymerization formula
100 parts of vinyl chloride
120 parts of deionized water
0.08 part of dispersion（Added by pure dispersant in terms of quality）
Initiation system cumyl peroxyneodecanoate, 0.1 part
0.08 part of chain extender emulsification system（Added by pure chain extender in terms of quality）
PH conditioning agent ammonium hydrogen carbonate, 0.001 part
Terminator diethyl hydroxylamine, 0.015 part.
Operating method：Polymeric kettle is rinsed well and coated after anti-fouling agent, and reactor is evacuated into -0.09MPa, according to
Above-mentioned polymerization formula adds deionized water, triggers system, dispersion, PH conditioning agents, chain extender emulsification system and vinyl chloride list
Body, while starting jacket of polymerization water-bath circulation, system temperature reaches setting value steadily in control polymeric kettle（46±0.5）℃
When, reaction starts timing；Terminator is added when polymerization system pressure drop △ P reach 0.03MPa during polymerisation 5h, 5 points are stirred
Unreacted monomer, emptying discharging, pulp centrifuged, boiled bed drying are reclaimed after clock.Polymerization gained resin basic performance is shown in Table 1.
Embodiment 2：
Material addition is as different from Example 1：Add 100 parts of deionized waters, 0.005 part of initiation system, 0.008
Part dispersion, 0.005 part of PH conditioning agent, 0.001 part of chain extender emulsification system and 100 parts of VCM and copolymerization list
Body, operating method is same as Example 1.Polymerization gained resin basic performance is shown in Table 1.
Embodiment 3：
Material addition is as different from Example 1：Add 200 parts of deionized waters, 1 part of initiation system, 1 part of dispersion
System, 2 parts of PH conditioning agents, 1 part of chain extender emulsification system and 100 parts of VCM and comonomer, operating method is with implementing
Example 1 is identical.Polymerization gained resin basic performance is shown in Table 1.
Embodiment 4：
Chain extender emulsification system as different from Example 1（Solid content 10.0%）：By 10 parts of chain extender phthalic acids two
Allyl ester is added to preformulation and obtained in polyvinyl alcohol water solution, and chain extension system is expanded without obvious lamination after stirring 60 minutes
Chain agent emulsification system, wherein polyvinyl alcohol water solution are that 3 parts of degree of polymerization are the polyethylene of solid content 35% that 200, alcoholysis degree is 50%
Alcohol, which is added to 87 parts of deionized waters and stirred, to be formed.Remaining is same as Example 1.Polymerization gained resin basic performance is shown in Table 1.
Embodiment 5：
Chain extender emulsification system as different from Example 1（Solid content 0.5%）：By 0.5 part of chain extender phthalic acid two
Allyl ester is added to preformulation and obtained in polyvinyl alcohol water solution, and chain extension system is expanded without obvious lamination after stirring 60 minutes
Chain agent emulsification system, wherein polyvinyl alcohol water solution are that 0.14 part of degree of polymerization is the poly- second of solid content 35% that 400, alcoholysis degree is 30%
Enol, which is added to 99.36 parts of deionized waters and stirred, to be formed.Remaining polymerization component and operating method are same as Example 1.
Polymerization gained resin basic performance is shown in Table 1.
Embodiment 6：
Chain extender emulsification system as different from Example 1（Solid content 20%）：By 20 parts of chain extender diallyl phthalates
Propyl ester is added to preformulation and obtained in polyvinyl alcohol water solution, and chain extension system obtains chain extension without obvious lamination after stirring 60 minutes
Agent emulsification system, wherein polyvinyl alcohol water solution are that 2.86 parts of degree of polymerization are the polyethylene of solid content 35% that 500, alcoholysis degree is 55%
Alcohol, which is added to 77.14 parts of deionized waters and stirred, to be formed.Remaining polymerization component and operating method are same as Example 1.It is poly-
Close gained resin basic performance and be shown in Table 1.
Embodiment 7：
Chain extender is divinylbenzene as different from Example 1, and dispersion is：By the degree of polymerization in 1400, alcoholysis degree
In 70% high alcoholysis degree polyvinyl alcohol（Solid content 5%）/ the degree of polymerization is the polyvinyl alcohol with low alcoholysis level that 350, alcoholysis degree is 45%
（Solid content 35%）/ methyl substitution is that methylcellulose/hydroxypropyl substitution value that 1.9, content is 32% is that 0.25, content is
10%th, methyl substitution be 1.8, content be 20% hydroxypropyl methyl cellulose by pure dispersant mass ratio 1.5：0.5：0.5：
0.5 uniform mixing.Remaining is same as Example 1.Polymerization gained resin basic performance is shown in Table 1.
Embodiment 8：
Chain extender divinylbenzene as different from Example 1, dispersion is：The degree of polymerization is existed in 1600, alcoholysis degree
90% high alcoholysis degree polyvinyl alcohol（Solid content 5%）/ the degree of polymerization is the polyvinyl alcohol with low alcoholysis level that 300, alcoholysis degree is 40%（Gu
Content 35%）/ methyl substitution is that methylcellulose/hydroxypropyl substitution value that 1.6, content is 30% is that 0.1, content is 4%, first
Base substitution value be 1.0, content be 19% hydroxypropyl methyl cellulose by pure dispersant mass ratio 2：1：1：0.8 uniform mixing.Breast
Change system addition is 0.2 part, and polymerization temperature is 50 DEG C, and remaining is same as Example 1.Polymerization gained resin basic performance is shown in Table
1。
Embodiment 9：
Chain extender divinylbenzene as different from Example 1, dispersion is：The degree of polymerization is existed in 1000, alcoholysis degree
80% high alcoholysis degree polyvinyl alcohol（Solid content 5%）/ the degree of polymerization is the polyvinyl alcohol with low alcoholysis level that 400, alcoholysis degree is 50%（Gu
Content 35%）/ methyl substitution be methylcellulose/hydroxypropyl substitution value that 1.7, content is 27% be 0.31, content be 12%,
Methyl substitution be 2.0, content be 30% hydroxypropyl methyl cellulose by pure dispersant mass ratio 1.5：1.5：2.5：0.5 is equal
Even mixing.Emulsification system addition is 0.2 part, and polymerization temperature is 50 DEG C, and remaining is same as Example 1.Polymerization gained resin base
This performance is shown in Table 1.
Comparative example 1：
The surface dispersant used in chain extender emulsification treatment is the degree of polymerization in 1000, alcoholysis degree as different from Example 1
Polyvinyl alcohol between 70%, 0.08 part of diallyl phthalate emulsification system is added to other reagent and additive in polymerization
In polymerization system.Remaining is same as Example 1.Polymerization gained resin basic performance is shown in Table 1.
Comparative example 2：
The surface dispersant used in chain extender emulsification treatment is the degree of polymerization in 1600, alcoholysis degree as different from Example 1
Polyvinyl alcohol between 90%, polymerization system is added to by 0.15 part of diallyl phthalate with other reagent and additive in polymerization
In.Remaining is same as Example 1.Polymerization gained resin basic performance is shown in Table 1.
Comparative example 3：
Chain extender is without emulsification treatment as different from Example 1, directly by 0.08 part of diallyl phthalate third
Ester is added in polymerization system with other reagent and additive in polymerization.Remaining is same as Example 1.Polymerization gained resin basic performance is shown in Table 1.
Comparative example 4：
Dispersion as different from Example 1：High alcoholysis degree polyethylene by the degree of polymerization in 1200, alcoholysis degree 80%
Alcohol（Solid content 5%）/ methyl substitution is that methylcellulose/hydroxypropyl substitution value that 1.7, content is 30% is that 0.18, content is
8%th, methyl substitution be 1.5, content be 25% hydroxypropyl methyl cellulose by pure dispersant mass ratio 1.5：1：0.5 is uniform mixed
Close.Remaining is same as Example 1.Polymerization gained resin basic performance is shown in Table 1.
Comparative example 5：
Dispersion as different from Example 1：High alcoholysis degree polyethylene by the degree of polymerization in 1200, alcoholysis degree 80%
Alcohol（Solid content 5%）Hydroxypropyl substitution value is that 0.18, content is that 8%, methyl substitution is the hydroxypropyl methyl that 1.5, content is 25%
Cellulose presses pure dispersant mass ratio 1.5：1 uniform mixing.Remaining is same as Example 1.Polymerization gained resin basic performance is shown in
Table 1.
Comparative example 6：
Chain extender is without emulsification treatment as different from Example 1, directly by 0.08 part of divinylbenzene with other
Reagent and additive in polymerization is added in polymerization system.Remaining is same as Example 1.Polymerization gained resin basic performance is shown in Table 1.
Comparative example 7：
Chain extender emulsification is using one of main dispersant used in suspension polymerization of VC system, i.e., high poly- in this comparative example
One quasi-polyethylene alcohol of right, high alcoholysis degree carries out polyvinyl alcohol design parameter used in chain extender emulsification system preparation, this example
For the degree of polymerization 2000, alcoholysis degree 80%, solid content 5%, prepare component and process is same as Example 1.
The synthesis of high polymerization degree resin, polymerization component and technique and embodiment 1 are carried out using the chain extension system of above-mentioned preparation
It is identical.Polymerization gained resin basic performance is shown in Table 1.
Comparative example 8：
One of main dispersant used in suspension polymerization of VC system, i.e. cellulose ethers is used to disperse in this comparative example
It is hydroxypropyl substitution value that agent, which carries out hydroxypropyl methyl cellulose design parameter used in chain extender emulsification system configuration, this example,
0.25th, content is 10.0%, and methyl substitution is that 1.9, content is 29%, solid content 3%, prepares component and process and the phase of embodiment 1
Together.
The synthesis of high polymerization degree resin, polymerization component and technique and embodiment 1 are carried out using the chain extension system of above-mentioned preparation
It is identical.Polymerization gained resin basic performance is shown in Table 1.
The resin polymerization yield of table 1 and the performance test results
As can be seen from the above table, chain extender is gathered with low polymerization degree, the low alcoholysis level commonly used in suspension polymerization of VC
Vinyl alcohol dispersant carries out emulsification treatment, the chain extender emulsification system that can be stablized, this expansion as surfactant
Chain agent emulsification system will not have a negative impact to polymerization system stability, and be gathered using common in polymerization initial stage with other
The technique that auxiliary agent is disposably added to polymerization system is closed, operating procedure is simple, and obtained PVC with high " flake " number
Significantly reduce；Chain extender does not carry out the emulsification treatment of this surfactant in comparative example 6, and obtained resin " flake " number is obvious
It is more；Other class dispersants in suspension polymerization of VC are used to be carried out as surfactant at chain extender emulsification in comparative example
Reason, and the same polymeric technique disposably added using polymerization initial stage, also fail to effectively cause resin " flake " number reduction.This is
Because " flake " often is failed to melt in process and formed by supramolecular, and has carried out the chain extension of reasonable emulsification treatment
Agent sufficiently can uniformly dissolve each other rapidly with VCM, will not local concentration it is too high and polymerize and form supramolecular, and then subtract
The probability of formation " flake " is lacked.
Comparison by implementing row and comparative example can be seen that the chain extender emulsifying technology of invention proposition and in height polymerization
The polymerization technique spent in polyvinyl chloride resin, i.e. chain extender are carried out after emulsification treatment, by the way of polymerization technique is added initial stage, in reality
Easily operated in the production of border, control it is steady, using this technology polymerize obtained by high polymerization degree resin processing characteristics it is excellent, particularly
" flake " number is few, products appearance is better than general product, solves and now commonly uses that high polymerization degree resin " flake " number is more, product
The undesirable shortcoming of outward appearance, can be widely applied to encapsulant, sole materials, heat-resistant hose, high-grade CABLE MATERIALS, film of evaporating brine, soil
It is a kind of method for synthesizing high-quality HPVC resins in terms of work film.
The above described is only a preferred embodiment of the present invention, being not the limitation for making other forms to the present invention, appoint
What those skilled in the art changed or be modified as possibly also with the technology contents of the disclosure above equivalent variations etc.
Imitate embodiment.But it is every without departing from technical solution of the present invention content, the technical spirit according to the present invention is to above example institute
Any simple modification, equivalent variations and the remodeling made, still fall within the protection domain of technical solution of the present invention.
Claims (5)
1. a kind of preparation method of high degree of polymerization of polyvinyl chloride resin, it is characterised in that specifically preparation technology is： 1）Chain extension
Agent is emulsified：It is 0.1% ~ 20%, surface-active by chain extender, surfactant, deionized water stirring chemical conversion chain extender content
Agent content obtains chain extender emulsification system for 0.05% ~ 2.0% homogeneous latex emulsion, and wherein surfactant is the degree of polymerization 200
Between ~ 500, polyvinyl alcohol of the alcoholysis degree between 30% ~ 55%； 2）HPVC polymerize：Reactor is evacuated to-
After 0.09MPa, 100 ~ 200 parts of deionized waters of addition, 0.005 ~ 1 part of initiation system, 0.005 ~ 1 based on pure weight of material part
Part dispersion, 0.005 ~ 2 part of pH adjusting agent, 0.001 ~ 1 part of chain extender emulsification system and 100 parts of VCM and
Comonomer, while start chuck water-bath circulation, system temperature in control polymeric kettle, when the reaction temperature for reaching 20 ~ 60 DEG C
When, reaction starts timing；When polymerization reaches process endpoint, adding terminator stops reaction；After stirring 2 ~ 10 minutes
Monomer is reclaimed, then emptying discharging, centrifugation slurry, drying；
Step 2）Described in dispersion be polyvinyl alcohol and cellulose in mass ratio 1:（0.5~1）Mixed dispersant,
Wherein polyvinyl alcohol is that the degree of polymerization exists in polyvinyl alcohol of 1000 ~ 1600, alcoholysis degree between 70% ~ 90% and the degree of polymerization
Between 300 ~ 400, polyvinyl alcohol of the alcoholysis degree between 40% ~ 50% in mass ratio 1：3~3 ：1 mixture；Fiber
Element be methyl substitution be the methylcellulose and hydroxypropyl substitution value that 1.6 ~ 1.9, content is 27% ~ 32% be 0.1 ~ 0.31,
Content is that 4.0% ~ 12.0%, methyl substitution is that the hydroxypropyl methyl cellulose that 1.0 ~ 2.0, content is 19% ~ 30% presses matter
Amount is than being 1：5~5 ：1 compound cellulose.
2. a kind of preparation method of high degree of polymerization of polyvinyl chloride resin according to claim 1, it is characterised in that：Step
Rapid 1）Described in chain extender emulsification system in chain extender content be 0.5% ~ 10%.
3. a kind of preparation method of high degree of polymerization of polyvinyl chloride resin according to claim 1, it is characterised in that：Step
Rapid 1）Described surfactant be the degree of polymerization be 200 ~ 300, alcoholysis degree be 45% ~ 55% between polyvinyl alcohol.
4. a kind of preparation method of high degree of polymerization of polyvinyl chloride resin according to claim 1, it is characterised in that：Step
Rapid 2）Described in chain extender emulsification system addition parts by weight with pure chain extender add quality be calculated as 0.01 ~ 0.5 part.
5. a kind of preparation method of high degree of polymerization of polyvinyl chloride resin according to claim 1, it is characterised in that：Institute
The chain extender stated is diallyl phthalate or divinylbenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410257523.4A CN105273119B (en) | 2014-06-11 | 2014-06-11 | A kind of preparation method of high degree of polymerization of polyvinyl chloride resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410257523.4A CN105273119B (en) | 2014-06-11 | 2014-06-11 | A kind of preparation method of high degree of polymerization of polyvinyl chloride resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105273119A CN105273119A (en) | 2016-01-27 |
| CN105273119B true CN105273119B (en) | 2017-08-29 |
Family
ID=55143009
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410257523.4A Active CN105273119B (en) | 2014-06-11 | 2014-06-11 | A kind of preparation method of high degree of polymerization of polyvinyl chloride resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105273119B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105968272B (en) * | 2016-06-28 | 2019-04-16 | 杭州电化集团有限公司 | The preparation method of Delustering Polychloroethylene |
| CN108084607B (en) * | 2017-12-29 | 2019-12-06 | 常州市宏杉新材料有限公司 | Cable material containing composite gel with self-repairing function and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101386661A (en) * | 2008-09-16 | 2009-03-18 | 浙江巨化股份有限公司电化厂 | Method for preparing polychloroethylene with high polymerization degree |
| CN103289003A (en) * | 2013-05-23 | 2013-09-11 | 苏州富通高新材料科技股份有限公司 | HPVC (High Degree of Polymerization) resin material and preparation method thereof |
| CN103360536A (en) * | 2012-03-31 | 2013-10-23 | 中国石油化工股份有限公司 | Polyvinyl chloride production method adding chain extender to match with later-stage heating process |
| CN103435734A (en) * | 2013-08-28 | 2013-12-11 | 贵州开磷遵义碱厂 | Preparation method of highly polymerized polyvinyl chloride resin chain extender emulsion |
-
2014
- 2014-06-11 CN CN201410257523.4A patent/CN105273119B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101386661A (en) * | 2008-09-16 | 2009-03-18 | 浙江巨化股份有限公司电化厂 | Method for preparing polychloroethylene with high polymerization degree |
| CN103360536A (en) * | 2012-03-31 | 2013-10-23 | 中国石油化工股份有限公司 | Polyvinyl chloride production method adding chain extender to match with later-stage heating process |
| CN103289003A (en) * | 2013-05-23 | 2013-09-11 | 苏州富通高新材料科技股份有限公司 | HPVC (High Degree of Polymerization) resin material and preparation method thereof |
| CN103435734A (en) * | 2013-08-28 | 2013-12-11 | 贵州开磷遵义碱厂 | Preparation method of highly polymerized polyvinyl chloride resin chain extender emulsion |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105273119A (en) | 2016-01-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3804881A (en) | Polymerization using varying monomer concentration | |
| JP5181113B2 (en) | Process for the production of polymers stabilized with protective colloids and apparatus for carrying out said process | |
| CN104693636B (en) | It is a kind of that there is the polymerization for improving ABS graft copolymer conversion ratio | |
| US3563946A (en) | Process for latex manufacture | |
| JPH06206950A (en) | Production of graft copolymer latex of core/shell disperse particle with improved phase bond between core and shell | |
| CN106832064B (en) | A kind of two (2- ethyl hexyl) ester initiator of emulsion-type dicetyl peroxydicarbonate and its application | |
| CN101191003A (en) | High transparence MBS resin composition with excellent impact property | |
| CN102382235B (en) | Acrylic emulsion, preparation method and application thereof | |
| JPH0433285B2 (en) | ||
| CN105916892A (en) | Vinyl chloride-based polymer and method for producing same | |
| CN104250335B (en) | A kind of production method of polychloroethylene with high polymerization degree resin | |
| CN104877056B (en) | Polyvinyl chloride resin preparing method capable of reducing membranes of surfaces of particles and improving porosity | |
| JPH03181507A (en) | Acrylonitrilebutadiene rubber copolymer having selected final composition high in linked acrylonitrile content and its continuous polymerization | |
| CN105273119B (en) | A kind of preparation method of high degree of polymerization of polyvinyl chloride resin | |
| CN103360536A (en) | Polyvinyl chloride production method adding chain extender to match with later-stage heating process | |
| KR101056958B1 (en) | Method for preparing vinyl chloride polymer by additional addition of water soluble initiator | |
| CA1056542A (en) | Process for forming acrylic elastomer containing interpolymer particles by emulsion polymerization | |
| WO2006039860A1 (en) | A preparation method of small particle sized polybutadiene latex used for the production of abs | |
| DE102011005388A1 (en) | Process for the preparation of polymers by emulsion or suspension polymerization | |
| CN102040697A (en) | Method for preparing adhesive purpose chloroprene rubber | |
| CN105273111B (en) | A kind of method of stripper plant fouling in reduction Production of PVC | |
| KR840001740B1 (en) | Process for preparing copolymers | |
| EP1420034B1 (en) | Process for recovery of residual ethylene from the production of vinylester-ethylene copolymers | |
| US2624724A (en) | Polymerization of vinyl chloride in an aqueous emulsion | |
| CN108395493B (en) | A kind of synthetic method of the polychloroethylene with high polymerization degree based on pickering emulsion type chain extender |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |