CN106317286A - Matting polyvinyl chloride resin synthetic method - Google Patents
Matting polyvinyl chloride resin synthetic method Download PDFInfo
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- CN106317286A CN106317286A CN201510336231.4A CN201510336231A CN106317286A CN 106317286 A CN106317286 A CN 106317286A CN 201510336231 A CN201510336231 A CN 201510336231A CN 106317286 A CN106317286 A CN 106317286A
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Abstract
The invention relates to a matting polyvinyl chloride resin synthetic method, which belongs to the technical field of PVC polymerization. The preparation technology comprises the following steps: 1) feeding in a polymerization kettle according to a polymerization formula of matting polyvinyl chloride and heating the material to the temperature of 62-64 DEG C for polymerization at constant temperature; and 2) when the conversion rate of a vinyl chloride monomer in the polymerization kettle reaches 56-59% by the polymerization at the constant temperature, heating the temperature of the material in the polymerization kettle to 12-15 DEG C, and centrifuging a slurry until the reaction is complete and drying the material to obtain PVC resin. In the invention, a temperature control technology of constant temperature polymerization of the matting polyvinyl chloride resin can be changed, a temperature-changing polymerization technology is employed, so that compared with the traditional matting resin, and the product produced by the matting polyvinyl chloride resin has less fisheye, and uniform appearance delustring.
Description
Technical field
The synthetic method of a kind of Delustering Polychloroethylene, belongs to PVC polymerization technique field.
Background technology
PVC is one of five big general-purpose plastics, increasingly extensive along with PVC application, the development trend of PVC resin by generalization to high performance, professional development.In recent years, in fields such as packaging, cable, building materials, vehicle, furniture, medical treatment, it is desirable to PVC goods have relatively low lustrous surface, make the demand of delustring polyvinyl chloride resin day by day increase.
Reach the traditional diamond-making technique of extinction effect, such as acrylate coating, embossed surface, addition delustering agent or filler (such as inorganic filler or PE resin etc.), cannot meet the market requirement to high-quality delustring goods.Plastics in China processing enterprise is when producing high-grade delustring goods, commonly used special resin for dulling polyvinyl chloride, the measured special resin for dulling polyvinyl chloride of matter should possess and not damage processing characteristics, Conventional processing methods can be processed, and products appearance delustring is uniform, particularly " flake " number is few, to improve the market degree of recognition for high-quality delustring PVC resin and plastic goods.
The technique that suspension pvc resin manufacturer is typically chosen interpolation cross-linking agent is resin dedicated to synthesize delustring PVC.What cross-linking agent was that intramolecular has two or more double bonds can be with the second comonomer of chloroethylene copolymer, such as diallyl phthalate (DAP), diallyl maleate (DAM), triallyl cyanurate (TAIC), ethylene glycol bisthioglycolate methyl ester acrylate (EGDMA), glycerol two (methyl) acrylate, polyethyleneglycol diacrylate etc., one or more cross-linking agent are joined among general suspension polymerization of VC system, PVC molecule is made to form branch or the cross-linked structure insoluble in solvent, i.e. oxolane (THF) insoluble matter gel.The polyvinyl chloride resin using this part to crosslink reaction is processed, and under high temperature, gel structure deforms, rotates and is orientated in continuous phase colloidal sol, and along with the reduction of temperature, material is changed into elastomeric state and glassy state by viscous state.Due to gel and colloidal sol difference structurally, in transition process, there is the biggest difference with colloidal sol continuous phase in the lax and viscoelasticity of gel structure, so that product surface produces small concavo-convex fluctuating.When light is irradiated to product surface, there is diffuse-reflectance, reduce the direct reflection on surface, so that product surface shows delustring performance after processing.
At present, manufacturer majority uses cross-linking agent all to add or in polymerization process, the suspension process of (or certain flow rate pumps into), to synthesize delustring polyvinyl chloride resin, does not have particular/special requirement to the temperature control of polymerization, dispersion, initiator system etc. in batches at the polymerization initial stage.This relatively simple production technology, device is changed less, technology controlling and process is easy so that resins synthesis device can add cross-linking agent substantially in original production process can synthesize delustring polyvinyl chloride resin.But, the extinction effect of goods is undesirable, easily occurs that the phenomenon that poor processability, delustring are uneven, particularly " flake " are many.
Japan develops quickly in terms of Corvic synthesis.United States Patent (USP) " the Process of publication number US 4816539
For producing vinyl chloride copolymer " in; inventor proposes in general suspension polymerization of VC system; add 0.1 ~ 10% polyol type glycerol diacrylate class cross-linking agent not waited according to gel content needed for resin; and to the initiator of polymerization system, dispersant, temperature control etc. without particular/special requirement, can prepare show delustring uniformly, " flake " several less delustring material resin.The method employs polyol type cross-linking agent rarely needed in industry, polymerization system stability is had negative effect, need adjust dispersant dosage, and this cross-linking agent price is higher, add production cost.
US
5248733 United States Patent (USP)s " Process for producing matter vinyl
Chloride copolymers " in; inventor points out that adding too much cross-linking agent in suspension polymerization system can affect processing characteristics and produce a large amount of " flake "; less cross-linking agent does not then reach the effect of delustring; so proposing to add the cross-linking agent of 0.005 ~ 0.2% in system, and coordinate the delustering agent of addition 0.1 ~ 20%.Wherein delustering agent is the cross-linked copolymer of the styrene containing 3 ~ 25% gels-(methyl) esters of acrylic acid, grinds to form fine powder, polymerization join in polymerization system before starting and stir to powder be fully dissolved or dispersed in Vinyl Chloride Monomer mutually in, then constant temperature polymerization.The core of this patent is to add the high polymer delustering agent of esters of acrylic acid on the basis of conventional polymerization technique in polymerization system, but this high polymer powder easily causes polymerization system unstable in actual production, light then resin particle is irregular, weight the most then polymerization system unstability, therefore polymer dispersion system is required harshness.
US
5614593 United States Patent (USP)s " Preparation of matter vinyl
Chloride polymer and composition thereof " in; inventor proposes in vinyl chloride suspension system; polymerization adds the diallyl phthalate (DAP) of 0.05 ~ 0.25% before starting; when conversion ratio to be polymerized reaches 20 ~ 60%; add two (methyl) acrylic acid dihexyl of 0.01 ~ 0.15%, and to the initiator of polymerization system, dispersant, temperature control etc. without particular/special requirement.This patent essence is to be added by the substep of cross-linking agent and reduce the local concentration of cross-linking agent, reach the uniform purpose of resin crosslinks, resin delustring outward appearance can be improved to a certain extent, but two kinds of different cross-linking agent add operating procedure difficulty in the substep addition of different polymerization stages.
CN1390865A Chinese patent " a kind of special resin for dulling polyvinyl chloride and preparation method thereof ", inventor proposes during suspension method prepares delustring polyvinyl chloride resin, add 0.01 ~ 5%(and account for vinyl chloride quality) diene or the second component monomer of polyene structure, and start at the uniform velocity to join in system with polymerization, the delustring preparing gel content 10 ~ 30% is resin dedicated.This technology can prepare the polyvinyl chloride resin of extinction effect, but resin " flake " is more, belongs to the technology producing delustring polyvinyl chloride resin earlier.
Summary of the invention
The technical problem to be solved in the present invention is: overcome the deficiencies in the prior art, it is provided that the synthetic method of the Delustering Polychloroethylene that a kind of surface dulling is uniformly, " flake " number is few.
The technical solution adopted for the present invention to solve the technical problems is: the synthetic method of this Delustering Polychloroethylene, it is characterised in that preparation technology is:
1) feed intake to polymeric kettle according to the polymerization formula of dulling polyvinyl chloride and be warming up to 62 DEG C ~ 64 DEG C constant temperature polymerizations；
2) when Vinyl Chloride Monomer conversion ratio reaches 55% ~ 59% in constant temperature polymerization makes polymeric kettle, again promote temperature of charge 12 DEG C ~ 15 DEG C in polymeric kettle, until reaction terminates pulp centrifuged and is dried, obtain polyvinyl chloride resin.
The present invention is first according to general delustring polyvinyl chloride resin polymerization process's step, polymeric kettle is rinsed well, coating anti-fouling agent, deionized water, initiator system, dispersion, cross-linking agent, pH adjusting agent is added according to polymerization formula, Vinyl Chloride Monomer is added after being evacuated to certain vacuum degree, cold stir about 2 ~ 10 minutes, be warming up to the thermostatic polymerization of technological requirement；Then, when constant temperature polymerization makes system conversion ratio reach to a certain degree, promote in polymeric kettle temperature of charge to after predetermined value, react again and drop to technology controlling and process point addition terminator to pressure, after stirring 2 ~ 10 minutes, reclaim unreacted monomer, pulp centrifuged and be dried, obtain polyvinyl chloride resin.The above-mentioned thermostatic polymerization being warming up to technological requirement, reaction temperature can be selected according to the requirement of resin polymerization degree, tradition PVC polymerization technique can carry out constant temperature polymerization at 20 ~ 80 DEG C, but during the polymerization of front end constant temperature, the processing step of constant temperature polymerization is identical with the conventional process of general process for suspension polymerization in the alternating temperature technique of the present invention, it is critical only that the selection of this constant temperature polymerization temperature, the polymerization temperature of early stage of the present invention needs at 62 DEG C ~ 64 DEG C, increasing extent of temperature, at 12 DEG C ~ 15 DEG C, strictly controls two kinds of rates of polymerization during polymerization by above-mentioned two sections of temperature.Successively two specific polymerization systems are defined in polymeric kettle under this rate of polymerization, this temperature is utilized to control in PVC macromolecule random sequence while obtaining the collocation of suitable molecular chain length at two kinds of content, and realize two kinds of content high molecular cooperations of random sequence PVC, thus it is accurately controlled gained PVC at required degree of crystallinity, too much " flake " that elimination Delustering Polychloroethylene is formed because adding its cross-linking agent as far as possible.
When constant temperature polymerization makes system conversion ratio promote polymerization system temperature when reaching 56% ~ 59%, and conversion ratio can make too much resin polymerization degree be greatly lowered and make the transition less than 56%, does not then reach the purpose effectively reducing resin " flake " number when conversion ratio is higher than 59%.
Promote polymerization system temperature 12 DEG C ~ 15 DEG C, can close jacket water (J.W.) circulation relies on heat of polymerization to promote system temperature, chuck water temperature can also be promoted and promote system temperature, and in order to save energy resource consumption and reduce production cost, preferably be off jacket water (J.W.) circulation and rely on heat of polymerization to promote the way of system temperature.
Preferably, in the lifting polymeric kettle described in step 2, the heating rate of temperature of charge is 4 DEG C/min ~ 5 DEG C/min.In the present invention, the significantly rising of polymerization temperature makes the high molecular chain length of PVC shorten, and will necessarily there is the transition length between both front and back average chain length in temperature-rise period.Heating rate is then the content controlling these PVC with transition chain length.Under this heating rate, ensure that the combination of gained polyvinyl chloride resin both front and back PVC performance, the collocation of both performances will not be affected the most again because the PVC of too much transition chain length exists, be further ensured that the elimination of " flake ".
Preferably, described in step 2 again promote temperature time Vinyl Chloride Monomer conversion ratio be 57% ~ 58%.Heating up when this conversion ratio, the delustring performance of PVC, processing characteristics and flake eliminate the unification reaching optimal, and overall performance is optimal.
The polymerization formula of described dulling polyvinyl chloride includes deionized water 100 ~ 150 parts, initiator system 0.01 ~ 0.2 part, dispersion 0.03 ~ 0.5 part, cross-linking agent 0.005 ~ 1 part, Vinyl Chloride Monomer 100 parts by weight.The polymerization formula of dulling polyvinyl chloride can select this kind of traditional formula, and traditional formula can be polymerized by the polymerization technique of the present invention, and traditional formula gained delustring PVC flake number is greatly reduced.
Described cross-linking agent be in diallyl phthalate, diallyl maleate, divinylbenzene, triallyl cyanurate, ethylene glycol bisthioglycolate methyl ester acrylate, glycerol two (methyl) acrylate or polyethyleneglycol diacrylate any one, two or more arbitrary proportion mixture.Above-mentioned cross-linking agent all can play the effect of delustring in delustring PVC.
Preferably, described cross-linking agent is ethylene glycol bisthioglycolate methyl ester acrylate, glycerol two (methyl) acrylate or polyethyleneglycol diacrylate.The present invention is when arranging in pairs or groups this preferred cross-linking agent, and extinction effect and flake eradicating efficacy are more preferable.
Preferably, described cross-linking agent is disposable after polymerization kettle temperature raising to constant temperature is polymerized adds the 72% ~ 79% of its total addition, and in lifting polymeric kettle, after temperature of charge, property adds surplus again.The present invention can use any traditional cross-linking agent feed postition, all can reach more preferable flake eradicating efficacy on the basis of original.But the present invention is under this cross-linking agent Adding Way, extinction effect and flake eradicating efficacy can be more preferable, and flake number only has the present invention to use the 1/2 ~ 2/3 of conventional cross-linking agent feed postition.
Preferably, described initiator system is 2,2'-Azobis(2,4-dimethylvaleronitrile) and the mixture of di-isopropyl peroxydicarbonate 1:3.2 ~ 3.4 in mass ratio.Initiator system can use any traditional delustring PVC suspension polymerisation initiator, although is not the key inventive point of the present invention, but flake number only has the present invention to use the 80% ~ 85% of tradition initiator system when using this initiator system.
Preferably, described dispersion is the mixture of polyvinyl alcohol and hydroxypropyl methyl cellulose 1:13 ~ 14.5 in mass ratio, the degree of polymerization of described polyvinyl alcohol 800 ~ 2000, alcoholysis degree is between 70% ~ 90%, the hydroxypropyl substitution value of described hydroxypropyl methyl cellulose is 0.1 ~ 0.31, content is 4.0% ~ 12.0%, and methyl substitution is 1.0 ~ 2.0, content is 19%～30%.In the present invention, dispersion can use any traditional delustring PVC suspension polymerisation dispersion, but when using this dispersion, owing to the PVC of the transition chain length in temperature-rise period disperses evenly, flake number only has the present invention to use the 65% ~ 70% of tradition initiator system.
Vinyl Chloride Monomer is 1:(1 ~ 1.5 with the mass ratio of water)；Described traditional delustring PVC suspension polymerisation initiator is the free radical type initiator that can cause chloroethylene polymerization, such as azo and organic peroxide compounds, can be used alone with certain proportion and can also be made into compound system use, addition is about the 0.01 ~ 0.2% of monomer mass；Traditional compound system that delustring PVC suspension polymerisation dispersion is polyvinyl alcohol dispersant and cellulose ethers dispersant, addition is about the 0.03 ~ 0.5% of monomer mass；Described traditional delustring PVC suspension polymerisation cross-linking agent be intramolecular there are two or more double bonds can be with the activated monomer of chloroethylene copolymer, such as diallyl phthalate (DAP), diallyl maleate (DAM), divinylbenzene (DVB), triallyl cyanurate (TAIC), ethylene glycol bisthioglycolate methyl ester acrylate (EGDMA), glycerol two (methyl) acrylate, polyethyleneglycol diacrylate etc., can be used alone or multiple (including two kinds) is used in mixed way, i.e. previous property of polymerizable all adds, also during polymerizable in batches or certain flow rate pumps into；PH adjusting agent can use all kinds of alkaline conditioners according to the stability of polymerization system and particular/special requirement.
Compared with prior art, the synthetic method of the Delustering Polychloroethylene of the present invention is had the beneficial effect that in the present invention, change the temperature control process of tradition delustring polyvinyl chloride resin constant temperature polymerization, use alternating temperature polymerization technique, apply the goods that the matting resin of this technology aggregation gained is processed compared with tradition matting resin, " flake " number is few, outward appearance delustring is uniform, solve and now commonly use the shortcoming that delustring polyvinyl chloride resin goods " flake " number is more, products appearance is undesirable, can be widely used in the fields such as packaging, cable, building materials, vehicle, furniture, medical treatment.Actual production easily operates, controls steadily, can in suspension process delustring polyvinyl chloride resin commercial plant wide popularization and application.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be further described, and wherein embodiment 1 is most preferred embodiment.
Embodiment 1
Operational approach:
Polymeric kettle is rinsed well, coating anti-fouling agent also rinses, then evacuation, the deionized water of formula ratio, dispersant, initiator, pH adjusting agent and cross-linking agent is added according to polymerization formula, the Vinyl Chloride Monomer of formula ratio is added after evacuation, cold stir 10 minutes, be warming up to the first reaction temperature 63 DEG C and start timing.React about 3 hours, polymerisation conversion reaches to promote when 58% polymerization temperature in the kettle, increasing extent of temperature is 13 DEG C, heating rate is 4 DEG C/min ~ 5 DEG C/min, reaching the second reaction temperature 76 DEG C, polymerisation conversion reaches to add terminator when 80%, reclaims unreacted monomer after stirring 5 minutes, pulp centrifuged and be dried, obtain finished product polyvinyl chloride resin.According to GB/T 4611-2008 test resin " flake " number, polymerization technique and the results are shown in Table 1.
Component:
100 parts of vinyl chloride
Deionized water 150 parts
The dispersion degree of polymerization is 0.1 at 800 ~ 2000, alcoholysis degree polyvinyl alcohol between 70% ~ 90% and hydroxypropyl substitution value
~ 0.31, content be 4.0% ~ 12.0%, methyl substitution be 1.0 ~ 2.0, content be the mixture of 19%～30% hydroxypropyl methyl cellulose 1:13 ~ 14.5 in mass ratio, 0.08 part
The mixture of initiator system 2,2'-Azobis(2,4-dimethylvaleronitrile) and di-isopropyl peroxydicarbonate 1:3.2 ~ 3.4 in mass ratio, 0.07 part
PH adjusting agent ammonium hydrogen carbonate, 0.001 part
Cross-linking agent glycerol two (methyl) acrylate, 0.05 part
Terminator diethyl hydroxylamine, 0.01 part.
Embodiment 2
Increasing extent of temperature is 14 DEG C, reaches the second reaction temperature 77 DEG C, remaining operational approach and polymerization formula with embodiment 1.Polymerization technique and the results are shown in Table 1.
Embodiment 3
Increasing extent of temperature is 15 DEG C, reaches the second reaction temperature 78 DEG C, remaining operational approach and polymerization formula with embodiment 1.Polymerization technique and the results are shown in Table 1.
Embodiment 4
Promoting temperature in the kettle when polymerisation conversion reaches 56%, increasing extent of temperature is 13 DEG C, reaches the second reaction temperature 76 DEG C, remaining operational approach and polymerization formula with embodiment 1.Polymerization technique and the results are shown in Table 1.
Embodiment 5
Increasing extent of temperature is 12 DEG C, reaches the second reaction temperature 75 DEG C, remaining operational approach and polymerization formula with embodiment 4.Polymerization technique and the results are shown in Table 1.
Embodiment 6
Increasing extent of temperature is 15 DEG C, reaches the second reaction temperature 78 DEG C, remaining operational approach and polymerization formula with embodiment 4.Polymerization technique and the results are shown in Table 1.
Embodiment 7
Cross-linking agent DAP consumption is 0.10, is dividedly in some parts, and polymerization kettle temperature raising to constant temperature is disposable after being polymerized adds 0.075 part, is disposably adding surplus promoting in polymeric kettle after temperature of charge.Remaining operational approach and polymerization formula are with embodiment 1.Polymerization technique and the results are shown in Table 1.
Embodiment 8
First reaction temperature 62 DEG C, promotes temperature in the kettle when conversion ratio reaches 57%, and increasing extent of temperature is 15 DEG C and reaches the second reaction temperature 77 DEG C, and cross-linking agent is polyethyleneglycol diacrylate, and remaining operational approach and polymerization formula are with embodiment 7.Polymerization technique and the results are shown in Table 1.
Embodiment 9
Component:
100 parts of vinyl chloride
Deionized water 150 parts
The dispersion degree of polymerization is 0.1 at 800 ~ 2000, alcoholysis degree polyvinyl alcohol between 70% ~ 90% and hydroxypropyl substitution value
~ 0.31, content be 4.0% ~ 12.0%, methyl substitution be 1.0 ~ 2.0, content be the mixture of 19%～30% hydroxypropyl methyl cellulose 1:13 ~ 14.5 in mass ratio, 0.5 part
The mixture of initiator system 2,2'-Azobis(2,4-dimethylvaleronitrile) and di-isopropyl peroxydicarbonate 1:3.2 ~ 3.4 in mass ratio, 0.2 part
PH adjusting agent ammonium hydrogen carbonate, 0.001 part
Cross-linking agent ethylene glycol bisthioglycolate methyl ester acrylate (EGDMA), 1 part
Terminator diethyl hydroxylamine, 0.01 part
First reaction temperature 64 DEG C, promotes temperature in the kettle when conversion ratio reaches 59%, and increasing extent of temperature is 12 DEG C and reaches the second reaction temperature 76 DEG C, and remaining operational approach is with embodiment 7.Polymerization technique and the results are shown in Table 1.
Embodiment 10
Operational approach is with embodiment 1
Component:
100 parts of vinyl chloride
Deionized water 100 parts
Dispersion hydroxypropyl methyl cellulose, 0.03 part
Initiator system peroxy dicarbonate two-(2-ethylhexyl) ester/2,2'-Azobis(2,4-dimethylvaleronitrile), ratio is 1:3,0.01 part
PH adjusting agent ammonium hydrogen carbonate, 0.001 part
Cross-linker divinylbenzene (DVB), 0.005 part
Terminator diethyl hydroxylamine, 0.01 part
Polymerization technique and the results are shown in Table 1.
Embodiment 11
Promoting temperature in the kettle when polymerisation conversion reaches 56%, increasing extent of temperature is 15 DEG C, reaches the second reaction temperature 78 DEG C, and polymerization formula is with embodiment 10.Polymerization technique and the results are shown in Table 1.
Embodiment 12
Promoting temperature in the kettle when polymerisation conversion reaches 59%, increasing extent of temperature is 15 DEG C, reaches the second reaction temperature 78 DEG C, and polymerization formula is with embodiment 10.Polymerization technique and the results are shown in Table 1.
Comparative example 1
In this comparative example, without any cross-linking agent, using 63 DEG C of constant temperature polymerization to conversion ratios to reach 80% addition terminator and terminate polymerization, remaining is identical with embodiment 1 technique.Polymerization technique and the results are shown in Table 1.
Comparative example 2
In this comparative example, cross-linking agent is EGDMA, uses 63 DEG C of constant temperature polymerization to conversion ratios to reach 80% addition terminator and terminates polymerization, and i.e. without raising temperature in the kettle process, remaining is identical with embodiment 1 technique.Polymerization technique and the results are shown in Table 1.
Comparative example 3
In this comparative example, cross-linking agent is EGDMA, when using 63 DEG C of constant temperature polymerization to conversion ratios to reach 45%, promotes polymerization temperature in the kettle, and increasing extent of temperature is 13 DEG C, and remaining operational approach and polymerization formula are with embodiment 1.Polymerization technique and the results are shown in Table 1.
Comparative example 4
In this comparative example, cross-linking agent is EGDMA, when using 63 DEG C of constant temperature polymerization to conversion ratios to reach 75%, promotes polymerization temperature in the kettle, and increasing extent of temperature is 20 DEG C, and remaining operational approach and polymerization formula are with embodiment 1.Polymerization technique and the results are shown in Table 1.
Comparative example 5
In this comparative example, using 63 DEG C of constant temperature polymerizations, conversion ratio reaches to promote when 45% polymerization temperature in the kettle, and increasing extent of temperature is 15 DEG C, and remaining operational approach and polymerization formula are with embodiment 10.Polymerization technique and the results are shown in Table 1.
Comparative example 6
In this comparative example, using 63 DEG C of constant temperature polymerizations, conversion ratio reaches to promote when 75% polymerization temperature in the kettle, and increasing extent of temperature is 15 DEG C, and remaining operational approach and polymerization formula are with embodiment 10.Polymerization technique and the results are shown in Table 1.
Table 1 polymerization technique and " flake " number result
Note: in comparative example 2, resin polymerization degree is only 990, compares embodiment 1 ~ 9 resin average degree of polymerization 900 and has made the transition；In comparative example 5, resin polymerization degree is only 785, compares embodiment 10 ~ 12 resin average degree of polymerization 900 and the most makes the transition.
From table 1 embodiment it can be seen that the polymerization technique of the present invention, the resin that " flake " quantity is few, surface dulling is good can be obtained.Comparatively speaking, in comparative example, resin " flake " number is more, and extinction effect is undesirable.So, in conventional suspension method dulling polyvinyl chloride production technology, when polymerisation conversion reaches 56% ~ 59%, promoting polymerization system temperature 12 DEG C ~ 15 DEG C, it is few that polymerizable obtains " flake " number, has the matting resin of good delustring outward appearance.
The above, be only presently preferred embodiments of the present invention, is not the restriction that the present invention makees other form, and any those skilled in the art are changed possibly also with the technology contents of the disclosure above or are modified as the Equivalent embodiments of equivalent variations.But every without departing from technical solution of the present invention content, any simple modification, equivalent variations and remodeling above example made according to the technical spirit of the present invention, still fall within the protection domain of technical solution of the present invention.
Claims (9)
1. the synthetic method of a Delustering Polychloroethylene, it is characterised in that preparation technology is:
1) feed intake to polymeric kettle according to the polymerization formula of dulling polyvinyl chloride and be warming up to 62 DEG C ~ 64 DEG C constant temperature polymerizations；
2) when Vinyl Chloride Monomer conversion ratio reaches 56% ~ 59% in constant temperature polymerization makes polymeric kettle, again promote temperature of charge 12 DEG C ~ 15 DEG C in polymeric kettle, until reaction terminates pulp centrifuged and is dried, obtain polyvinyl chloride resin.
The synthetic method of a kind of Delustering Polychloroethylene the most according to claim 1, it is characterised in that: in the lifting polymeric kettle described in step 2, the heating rate of temperature of charge is 4 DEG C/min ~ 5 DEG C/min.
The synthetic method of a kind of Delustering Polychloroethylene the most according to claim 1, it is characterised in that: described in step 2 again promote temperature time Vinyl Chloride Monomer conversion ratio be 57% ~ 58%.
The synthetic method of a kind of Delustering Polychloroethylene the most according to claim 1, it is characterised in that: the polymerization formula of described dulling polyvinyl chloride includes deionized water 100 ~ 150 parts, initiator system 0.01 ~ 0.2 part, dispersion 0.03 ~ 0.5 part, cross-linking agent 0.005 ~ 1 part, Vinyl Chloride Monomer 100 parts by weight.
The synthetic method of a kind of Delustering Polychloroethylene the most according to claim 4, it is characterised in that: described cross-linking agent be in diallyl phthalate, diallyl maleate, divinylbenzene, triallyl cyanurate, ethylene glycol bisthioglycolate methyl ester acrylate, glycerol two (methyl) acrylate or polyethyleneglycol diacrylate any one, two or more arbitrary proportion mixture.
The synthetic method of a kind of Delustering Polychloroethylene the most according to claim 4, it is characterised in that: described cross-linking agent is ethylene glycol bisthioglycolate methyl ester acrylate, glycerol two (methyl) acrylate or polyethyleneglycol diacrylate.
7. according to the synthetic method of a kind of Delustering Polychloroethylene described in any one of claim 4 ~ 6, it is characterized in that: described cross-linking agent is disposable after polymerization kettle temperature raising to constant temperature is polymerized adds the 72% ~ 79% of its total addition, and in lifting polymeric kettle, after temperature of charge, property adds surplus again.
The synthetic method of a kind of Delustering Polychloroethylene the most according to claim 4, it is characterised in that: described initiator system is 2,2'-Azobis(2,4-dimethylvaleronitrile) and the mixture of di-isopropyl peroxydicarbonate 1:3.2 ~ 3.4 in mass ratio.
The synthetic method of a kind of Delustering Polychloroethylene the most according to claim 4, it is characterized in that: described dispersion is the mixture of polyvinyl alcohol and hydroxypropyl methyl cellulose 1:13 ~ 14.5 in mass ratio, the degree of polymerization of described polyvinyl alcohol 800 ~ 2000, alcoholysis degree is between 70% ~ 90%, the hydroxypropyl substitution value of described hydroxypropyl methyl cellulose is 0.1 ~ 0.31, content is 4.0% ~ 12.0%, and methyl substitution is 1.0 ~ 2.0, content is 19%～30%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107189018A (en) * | 2017-06-16 | 2017-09-22 | 杭州电化集团有限公司 | A kind of preparation method of high polymerization degree Delustering Polychloroethylene |
| CN107236065A (en) * | 2017-06-06 | 2017-10-10 | 滁州市宏源喷涂有限公司 | One kind avoids the method that " flake " is produced in PVC Production Process |
| CN108342169A (en) * | 2018-01-16 | 2018-07-31 | 江苏亚龙新材料科技有限公司 | A kind of pvc static-free glues band and preparation method thereof |
| CN108752515A (en) * | 2018-06-21 | 2018-11-06 | 江苏新汇烽塑胶有限公司 | A kind of high-strength polyvinyl chloride resin and preparation method thereof |
| CN110194814A (en) * | 2019-06-24 | 2019-09-03 | 中国石油化工股份有限公司 | A kind of extinction type Corvic and preparation method thereof |
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| CN107236065A (en) * | 2017-06-06 | 2017-10-10 | 滁州市宏源喷涂有限公司 | One kind avoids the method that " flake " is produced in PVC Production Process |
| CN107189018A (en) * | 2017-06-16 | 2017-09-22 | 杭州电化集团有限公司 | A kind of preparation method of high polymerization degree Delustering Polychloroethylene |
| CN108342169A (en) * | 2018-01-16 | 2018-07-31 | 江苏亚龙新材料科技有限公司 | A kind of pvc static-free glues band and preparation method thereof |
| CN108752515A (en) * | 2018-06-21 | 2018-11-06 | 江苏新汇烽塑胶有限公司 | A kind of high-strength polyvinyl chloride resin and preparation method thereof |
| CN110194814A (en) * | 2019-06-24 | 2019-09-03 | 中国石油化工股份有限公司 | A kind of extinction type Corvic and preparation method thereof |
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