CN107057216A - A kind of PVC modified plastics - Google Patents
A kind of PVC modified plastics Download PDFInfo
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- CN107057216A CN107057216A CN201611191735.2A CN201611191735A CN107057216A CN 107057216 A CN107057216 A CN 107057216A CN 201611191735 A CN201611191735 A CN 201611191735A CN 107057216 A CN107057216 A CN 107057216A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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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
- C08F114/00—Homopolymers 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
- C08F114/02—Monomers containing chlorine
- C08F114/04—Monomers containing two carbon atoms
- C08F114/06—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
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to plastic applications, a kind of PVC modified plastics are disclosed.To ensure that igelite product does not produce the excessive deformation of creep in long-term use, stress suffered by product is less than its critical stress value, present invention improves over the polymerization methodses of vinyl chloride, by control polymerization temperature and select suitable initiator and and catalyst, to control to polymerize carry out degree, the present invention is to cause the basic reason of Corvic creep and stress relaxation according to the sliding of the allosteric rearrangement and strand of polymerization macromolecule chain, and for the creep of same high polymer and stress relaxation, because both molecular motion essence is identical, the factor of all influence creeps will also influence stress relaxation, the present invention is elongated at the beginning in high polymer, when molecule is in unbalanced conformation, moved along the direction of external force and further eliminate internal stress to reduce.
Description
Technical field
The present invention relates to plastic applications, and in particular to a kind of PVC modified plastics.
Background technology
Polyvinyl chloride, English abbreviation PVC（Polyvinyl chloride）, it is VCM（vinyl chloride
Monomer, abbreviation VCM）In initiators such as peroxide, azo-compounds;Or Raolical polymerizable is pressed under light, heat effect
The polymer that mechanism is polymerized.Ryuron and vinyl chloride copolymer system are referred to as vinyl chloride resin.PVC is amorphous
The white powder of structure, the degree of branching is smaller, relative density 1.4 or so, 77-90 DEG C of glass transition temperature, and 170 DEG C or so start point
Solution, the stability to light and heat is poor, more than 100 DEG C or through long-time exposure in sunshine, will decompose and produce hydrogen chloride, go forward side by side
One step autocatalysis decompose, cause discoloration, physical and mechanical properties also declines rapidly, must be added in actual applications stabilizer with
Improve the stability to light and heat.Industrial PVC molecular weight is general in the range of 50,000-11 ten thousand, with larger polydispersion
Property, the reduction of molecular weight with polymerisation temperature and increase;Without definite melting point, 80-85 DEG C starts softening, and 130 DEG C are changed into viscoelastic state,
160-180 DEG C starts to be changed into viscous state;There are preferable mechanical performance, tensile strength 60MPa or so, impact strength 5-10kJ/
m2；There are excellent dielectric properties.PVC was once the general-purpose plastics of yield maximum in the world, using widely.Construction material,
Industrial product, commodity, flooring laminate, floor tile, artificial leather, tubing, electric wire, packaging film, bottle, expanded material, sealing material
It is widely used in terms of material, fiber.But be due to Corvic creep and stress relaxation phenomenon it is serious, it is impossible to do
For construction use and machine components high performance plastics, if it is possible to igelite is modified, raising polyvinyl chloride
The creep resistant and stress relaxation-resistant ability of resin, then igelite will be of great use on engineering plastics.
The content of the invention
In order to make igelite be applied on engineering plastics, change the invention provides a kind of polyvinyl chloride
Property plastics, its creep resistant and stress relaxation-resistant ability are significantly improved.
The present invention is achieved by the following technical solutions：
A kind of PVC modified plastics, including following modification procedure：
（1）Pure water, the liquefaction VCM that temperature is subzero 20-25 DEG C, dispersant are added in reactor, then added
Initiator and other auxiliary agents, initiator used are CuCl/2,2'- bipyridyls（bpy）, triphenyl phosphorus, with simple organic halogenation
Thing is initiator, and transition metal complex is halogen atom carrier, by redox reaction, is built between spike and dormancy kind
Reversible dynamic equilibrium is stood, the control to polymerisation is realized, monomer can be triggered to polymerize, chain tra nsfer, chain termination can be realized again,
Use metallic catalyst CuBr2、CuCl2Constitute the radical polymerization process that initiation system is carried out；
（2）Reactor is warming up to after 80-90 DEG C, temperature is too high, sub-chain motion resistance very little, stress quickly it is loose fall, Xiang Dan
The factors such as the transfer ability of body and monomer structure, temperature are relevant, and polyvinyl chloride chain transfer to monomer constant is highest in monomer
, about 10-3, its transfer rate depended primarily on to chloroethene far beyond the normal average degree of polymerization for terminating speed polyvinyl chloride
The speed constant of alkene transfer, PVC molecular weight is main by temperature control, adds polyvinyl alcohol and cellulose ethers as suspending stabilized
Agent, by crystalline high polymer, progressively cooling is made annealing treatment below 80 DEG C, and temperature is higher, the creep compliance and stress of high polymer
Relaxation modulus is faster with time development, is unfavorable for strengthening its creep resistance and stress relaxation-resistant ability, VCM occurs certainly
PVC granule is generated after base polymerisation, is persistently stirred, is stirred to the epigranular of particle, and can make what is just generated
Particle is suspended in water.
Further described as to such scheme, plasticizer used be dibutyl phthalate and three Benzophenones, with
Polyvinyl chloride resin Combination is good, and belongs to environment-friendlyplasticizer plasticizer.
Further described as to such scheme, filler used is molybdenum disulfide and graphitized fibre, it is possible to decrease polychlorostyrene
The creep of vinyl and stress relaxation rate.
Beneficial effects of the present invention：Become to ensure that igelite product does not produce excessive creep in long-term use
Shape, the stress suffered by product is less than its critical stress value, present invention improves over the polymerization methodses of vinyl chloride, by controlling to polymerize
Temperature and select suitable initiator and and catalyst, to control to polymerize carry out degree, the present invention is according to polymerization macromolecule
Allosteric rearrangement and the strand sliding of chain are to cause the basic reason of Corvic creep and stress relaxation, and just same
For the creep of high polymer and stress relaxation, because both molecular motion essence is identical, the factor of all influence creeps also must
Stress relaxation will be influenceed, the present invention is elongated at the beginning in high polymer, when molecule is in unbalanced conformation, along the side of external force
Always move and further eliminate internal stress to reduce, igelite of the invention can be used as engineering plastics.
Brief description of the drawings
It is that igelite creep and stress relaxation are comprehensive made from embodiment 1-3 respectively that 1,2,3 curves are corresponding in Fig. 1
Close performance and the relation of time, curve 4 is corresponding be existing igelite creep and stress relaxation combination property and when
Between relation.
Embodiment
The present invention is described further with reference to specific embodiment.
Embodiment 1
A kind of PVC modified plastics, including following modification procedure：
（1）Pure water, the liquefaction VCM that temperature is subzero 20 DEG C, dispersant are added in reactor, then adds and draws
Agent and other auxiliary agents are sent out, initiator used is CuCl/2,2'- bipyridyls（bpy）, triphenyl phosphorus, with simple organohalogen compounds
For initiator, transition metal complex is halogen atom carrier, by redox reaction, is set up between spike and dormancy kind
Reversible dynamic equilibrium, realizes the control to polymerisation, monomer can be triggered to polymerize, and chain tra nsfer, chain termination can be realized again, is made
Use metallic catalyst CuBr2、CuCl2Constitute the radical polymerization process that initiation system is carried out；
（2）Reactor is warming up to after 80 DEG C, temperature is too high, sub-chain motion resistance very little, stress quickly it is loose fall, to monomer
The factors such as transfer ability and monomer structure, temperature are relevant, and polyvinyl chloride chain transfer to monomer constant is highest in monomer, about
10-3, its transfer rate is depended primarily on far beyond the normal average degree of polymerization for terminating speed polyvinyl chloride to be turned to vinyl chloride
The speed constant of shifting, PVC molecular weight is main by temperature control, adds polyvinyl alcohol and cellulose ethers as suspension stabilizer,
By crystalline high polymer, progressively cooling is made annealing treatment below 80 DEG C, and temperature is higher, creep compliance and the stress pine of high polymer
Relaxation modulus is faster with time development, is unfavorable for strengthening its creep resistance and stress relaxation-resistant ability, VCM occurs freely
PVC granule is generated after base polymerisation, is persistently stirred, is stirred to the epigranular of particle, and that has just generated can be made
Grain is suspended in water.
Further described as to such scheme, plasticizer used be dibutyl phthalate and three Benzophenones, with
Polyvinyl chloride resin Combination is good, and belongs to environment-friendlyplasticizer plasticizer.
Further described as to such scheme, filler used is molybdenum disulfide and graphitized fibre, it is possible to decrease polychlorostyrene
The creep of vinyl and stress relaxation rate.
Embodiment 2
A kind of PVC modified plastics, including following modification procedure：
（1）Pure water, the liquefaction VCM that temperature is subzero 22 DEG C, dispersant are added in reactor, then adds and draws
Agent and other auxiliary agents are sent out, initiator used is CuCl/2,2'- bipyridyls（bpy）, triphenyl phosphorus, with simple organohalogen compounds
For initiator, transition metal complex is halogen atom carrier, by redox reaction, is set up between spike and dormancy kind
Reversible dynamic equilibrium, realizes the control to polymerisation, monomer can be triggered to polymerize, and chain tra nsfer, chain termination can be realized again, is made
Use metallic catalyst CuBr2、CuCl2Constitute the radical polymerization process that initiation system is carried out；
（2）Reactor is warming up to after 85 DEG C, temperature is too high, sub-chain motion resistance very little, stress quickly it is loose fall, to monomer
The factors such as transfer ability and monomer structure, temperature are relevant, and polyvinyl chloride chain transfer to monomer constant is highest in monomer, about
10-3, its transfer rate is depended primarily on far beyond the normal average degree of polymerization for terminating speed polyvinyl chloride to be turned to vinyl chloride
The speed constant of shifting, PVC molecular weight is main by temperature control, adds polyvinyl alcohol and cellulose ethers as suspension stabilizer,
By crystalline high polymer, progressively cooling is made annealing treatment below 80 DEG C, and temperature is higher, creep compliance and the stress pine of high polymer
Relaxation modulus is faster with time development, is unfavorable for strengthening its creep resistance and stress relaxation-resistant ability, VCM occurs freely
PVC granule is generated after base polymerisation, is persistently stirred, is stirred to the epigranular of particle, and that has just generated can be made
Grain is suspended in water.
Further described as to such scheme, plasticizer used be dibutyl phthalate and three Benzophenones, with
Polyvinyl chloride resin Combination is good, and belongs to environment-friendlyplasticizer plasticizer.
Further described as to such scheme, filler used is molybdenum disulfide and graphitized fibre, it is possible to decrease polychlorostyrene
The creep of vinyl and stress relaxation rate.
Embodiment 3
A kind of PVC modified plastics, including following modification procedure：
（1）Pure water, the liquefaction VCM that temperature is subzero 25 DEG C, dispersant are added in reactor, then adds and draws
Agent and other auxiliary agents are sent out, initiator used is CuCl/2,2'- bipyridyls（bpy）, triphenyl phosphorus, with simple organohalogen compounds
For initiator, transition metal complex is halogen atom carrier, by redox reaction, is set up between spike and dormancy kind
Reversible dynamic equilibrium, realizes the control to polymerisation, monomer can be triggered to polymerize, and chain tra nsfer, chain termination can be realized again, is made
Use metallic catalyst CuBr2、CuCl2Constitute the radical polymerization process that initiation system is carried out；
（2）Reactor is warming up to after 90 DEG C, temperature is too high, sub-chain motion resistance very little, stress quickly it is loose fall, to monomer
The factors such as transfer ability and monomer structure, temperature are relevant, and polyvinyl chloride chain transfer to monomer constant is highest in monomer, about
10-3, its transfer rate is depended primarily on far beyond the normal average degree of polymerization for terminating speed polyvinyl chloride to be turned to vinyl chloride
The speed constant of shifting, PVC molecular weight is main by temperature control, adds polyvinyl alcohol and cellulose ethers as suspension stabilizer,
By crystalline high polymer, progressively cooling is made annealing treatment below 80 DEG C, and temperature is higher, creep compliance and the stress pine of high polymer
Relaxation modulus is faster with time development, is unfavorable for strengthening its creep resistance and stress relaxation-resistant ability, VCM occurs freely
PVC granule is generated after base polymerisation, is persistently stirred, is stirred to the epigranular of particle, and that has just generated can be made
Grain is suspended in water.
Further described as to such scheme, plasticizer used be dibutyl phthalate and three Benzophenones, with
Polyvinyl chloride resin Combination is good, and belongs to environment-friendlyplasticizer plasticizer.
Further described as to such scheme, filler used is molybdenum disulfide and graphitized fibre, it is possible to decrease polychlorostyrene
The creep of vinyl and stress relaxation rate.
Contrast test
Respectively creep and stress are carried out using igelite made from the embodiment of the present invention and existing igelite
Relaxation all-round property testing, test result is drawn as shown in Figure 1.
Claims (3)
1. a kind of PVC modified plastics, it is characterised in that including following modification procedure：
（1）Pure water, the liquefaction VCM that temperature is subzero 20-25 DEG C, dispersant are added in reactor, then added
Initiator and other auxiliary agents, initiator used are CuCl/2,2'- bipyridyls（bpy）, triphenyl phosphorus, use metallic catalyst
CuBr2、CuCl2Constitute the radical polymerization process that initiation system is carried out；
（2）Reactor is warming up to after 80-90 DEG C, polyvinyl alcohol and cellulose ethers is added as suspension stabilizer, will crystallize
Progressively cooling is made annealing treatment high polymer below 80 DEG C, and VCM occurs to generate PVC after Raolical polymerizable
Grain, is persistently stirred, and stirs to the epigranular of particle, and the particle just generated can be made to be suspended in water.
2. a kind of PVC modified plastics according to claim 1, it is characterised in that plasticizer used is O-phthalic
Dibutyl phthalate and three Benzophenones.
3. a kind of PVC modified plastics according to claim 1, it is characterised in that filler used be molybdenum disulfide and
Graphitized fibre.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611191735.2A CN107057216A (en) | 2016-12-21 | 2016-12-21 | A kind of PVC modified plastics |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611191735.2A CN107057216A (en) | 2016-12-21 | 2016-12-21 | A kind of PVC modified plastics |
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| CN107057216A true CN107057216A (en) | 2017-08-18 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112277187A (en) * | 2020-10-23 | 2021-01-29 | 常德七星泰塑业有限公司 | Preparation method of PVC particles for PVC pipe fitting hot runner injection |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1389483A (en) * | 2002-06-25 | 2003-01-08 | 上海氯碱化工股份有限公司 | Suspension polymerization process of preparing polyvinyl chloride resin with high molecular weight |
| CN102492066A (en) * | 2011-12-08 | 2012-06-13 | 内蒙古宜化化工有限公司 | Method for preparing polyvinyl chloride by suspension polymerization |
| CN102558418A (en) * | 2012-01-10 | 2012-07-11 | 杭州电化集团有限公司 | Method for producing high-polymerization-degree polyvinyl chloride resin through suspension method |
| CN103980634A (en) * | 2014-05-31 | 2014-08-13 | 全椒祥瑞塑胶有限公司 | Polyvinyl chloride modified plastic |
| CN105801732A (en) * | 2014-12-31 | 2016-07-27 | 青岛威德森贸易有限公司 | Polyvinyl chloride suspension polymerization preparation method and feeding device |
-
2016
- 2016-12-21 CN CN201611191735.2A patent/CN107057216A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1389483A (en) * | 2002-06-25 | 2003-01-08 | 上海氯碱化工股份有限公司 | Suspension polymerization process of preparing polyvinyl chloride resin with high molecular weight |
| CN102492066A (en) * | 2011-12-08 | 2012-06-13 | 内蒙古宜化化工有限公司 | Method for preparing polyvinyl chloride by suspension polymerization |
| CN102558418A (en) * | 2012-01-10 | 2012-07-11 | 杭州电化集团有限公司 | Method for producing high-polymerization-degree polyvinyl chloride resin through suspension method |
| CN103980634A (en) * | 2014-05-31 | 2014-08-13 | 全椒祥瑞塑胶有限公司 | Polyvinyl chloride modified plastic |
| CN105801732A (en) * | 2014-12-31 | 2016-07-27 | 青岛威德森贸易有限公司 | Polyvinyl chloride suspension polymerization preparation method and feeding device |
Non-Patent Citations (1)
| Title |
|---|
| 唐黎明等: "《高分子化学》", 31 May 2000, 清华大学出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112277187A (en) * | 2020-10-23 | 2021-01-29 | 常德七星泰塑业有限公司 | Preparation method of PVC particles for PVC pipe fitting hot runner injection |
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Application publication date: 20170818 |