CN101104721A - Method for preparing nano hydrotalcite and nano calcium carbonate composite modified polyvinyl chloride resin - Google Patents
Method for preparing nano hydrotalcite and nano calcium carbonate composite modified polyvinyl chloride resin Download PDFInfo
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- CN101104721A CN101104721A CNA2007100698564A CN200710069856A CN101104721A CN 101104721 A CN101104721 A CN 101104721A CN A2007100698564 A CNA2007100698564 A CN A2007100698564A CN 200710069856 A CN200710069856 A CN 200710069856A CN 101104721 A CN101104721 A CN 101104721A
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- hydrotalcite
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Abstract
The invention relates to a preparation method of a polyvinyl chloride resin modified in compound by nano-hydrotalcite and nano-calcium carbonate. The steps of the preparation method are as follows: (1) 1.0g of the nano-hydrotalcite and 1.0 to 5.0g of the nano-calcium carbonate are added into 10 to 50g of deionized water containing 0.1 to 0.5g of dispersant, and are sheared and dispersed in ultrasonic or high speed for 10 to 60 min in the temperature of 20 to 100 DEG C, and the compound dispersion solution of the nano-hydrotalcite and the nano-calcium carbonate is obtained; (2) the compound dispersion solution of the nano-hydrotalcite and the nano-calcium carbonate, 0.05 to 0.50g of the initiator, 0.1 to 0.5g of the dispersant, 100g of vinyl chloride and 100 to 250g of the deionized water are put into a polymerization reactor and polymerized with the temperature being raised to 45 to 65 DEG C after being mixed for 10 to 60 min in room temperature until system pressure falls 0.5 to 2.5kg/cm2. Unreacted vinyl chloride is removed when the polymerization is finished, and then the polyvinyl chloride resin modified in compound by nano-hydrotalcite and nano-calcium carbonate is obtained after the material in the polymerization reactor is discharged, filtered and dried. The modified polyvinyl chloride prepared with the invention can become polyvinyl chloride compound material with uniform dispersed nano particles, improved thermal stability and mechanical property and low dense burning smoke through being processed.
Description
Technical field
The present invention relates to technical field of chemical engineering, relate in particular to the preparation method of a kind of nano hydrotalcite and nano calcium carbonate composite modified polyvinyl chloride resin.
Background technology
Polyvinyl chloride (PVC) has characteristics such as comprehensive mechanical property is good, fire-retardant, resistance to chemical attack, and can obtain hard, semi-rigid and flexible article with adding what of plasticizer loading, satisfies different service requirementss.But also there are shortcomings such as poor heat stability, the burning smoke density is big, the boardy product shock strength is lower in PVC.Because PVC contains unstable structure, under heating condition, easily remove the chain reaction of hydrogenchloride, can make material that undesirable colour-change takes place, and cause the decline of material mechanical performance, therefore, the necessary thermo-stabilizer that adds in PVC processing is as organic acid metal salt, organo-tin compound and alkali formula lead compound etc.The PVC goods can produce a large amount of smog in when burning, and at high temperature to remove hydrogenchloride, formation polyenoid and aromatic ring structure relevant with PVC for this.Smoke density when burning in order to reduce PVC can adopt metal oxide or organomolybdenum compound that PVC is carried out modification, but adopt the former to cause the decline of PVC material mechanical performance easily, and adopt the latter's cost higher.The method that organic impact modifier (as esters of acrylic acid, chlorinatedpolyethylene etc.) are added in the impact-resistant modified main employing of PVC, their anti-impact effect is more remarkable, but causes the decline of PVC product tensile strength easily.
Flourish nanotechnology since the eighties in 20th century provides new approach for developing high performance PVC material.The PVC nano composite material is becoming an emerging research field, and is attracting more and more researchers.Aspect the preparation of PVC nano composite material, nano-calcium carbonate is to use more inorganic nano material, this mainly is because the nano-calcium carbonate price is comparatively cheap, and when nano-calcium carbonate reaches the dispersion of nanoscale in the PVC matrix, can improve the mechanical property of PVC goods to a certain extent.But single use nano-calcium carbonate, the raising of PVC performance is mainly reflected in the shock strength aspect.
Nano hydrotalcite is a kind of new inorganic nano material, and its chemical constitution is: Mg
2+ 1-xAl
3+ x(OH
-)
2A
N- X/nMH
2O, wherein A
N-Be n valency negatively charged ion.Hydrotalcite has the laminate structure of similar polynite, and laminate is the double-metal hydroxide of positively charged, and interlayer is negatively charged ion and combination water.The nanometer laminate of hydrotalcite can be peeled off under certain condition, forms the separability nano material.On the other hand, by the control synthesis condition, also the direct hydrotalcite particle of synthesis of nano size can make the PVC nano composite material with the PVC compound tense without just peeling off of nanometer laminate.
React because nano hydrotalcite interlayer anion and layers of metal hydroxides plate can decompose the hydrogenchloride that produces with PVC, consume hydrogenchloride, thereby can play heat stabilization PVC.When nano hydrotalcite and organotin, the compound use of thermo-stabilizer such as calcium-zinc is compound or barium-zinc is compound, PVC thermally-stabilised had good synergy, demonstrate better thermostable effect.The bimetallic oxide that nano hydrotalcite and high temperature thereof (as at PVC goods combustion conditions) are decomposed to form also has vesicular structure, decapacitation absorbs PVC and decomposes outside the hydrogenchloride that produces, other volatile matter of PVC incendiary also there is adsorption, therefore can reduces the burning smoke density of PVC goods greatly.Therefore, nano hydrotalcite is a kind of good, multi-functional PVC properties-correcting agent.But the price of present commercial nano hydrotalcite is more expensive, has limited its widespread use in the PVC nano modification to a certain extent.The combining nano hydrotalcite is to the thermally-stabilised of PVC and press down the cigarette effect, and nano-calcium carbonate is to the impact-resistant modified effect of PVC, be expected to obtain a kind of PVC nano composite material of high comprehensive performance, simultaneously with price lower nano-calcium carbonate and the composite modified PVC of nano hydrotalcite, help reducing the production cost of modified PVC resin, for suitability for industrialized production provides the basis.
Nano hydrotalcite and nano-calcium carbonate hydrotalcite are reunited easily, simultaneously bigger with the polarity difference of PVC, in PVC, be difficult to reach the dispersion of uniform nanoscale, can not give full play to both modifying functions separately to PVC, therefore be necessary to adopt effective PVC/ inorganic nano-particle complex method, reach inorganic nano-particle evenly, low yardstick disperses, fully volatilization is separately to the modifying function of PVC.
In-situ polymerization is the novel method of preparation polymer/inorganic nanometer particle composite material, and it is to exist at (modification) nanoparticle, carries out monomeric polymerization in reactor, generates the polymer/inorganic nanometer particle composite material on the spot.Because inorganic nano-particle disperses in liquid phase (monomer or reaction medium) earlier, the viscosity of dispersion medium is little, dispersion means many (ultrasonic, high-speed stirring shearing etc.), simultaneously can utilize polymerization process again to the effect of agglomeration nano dispersion of particles, therefore, adopt in-situ polymerization often can reach than the dispersion effect of the better inorganic nano-particle of melt-processed in polymkeric substance.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of nano hydrotalcite and nano calcium carbonate composite modified polyvinyl chloride resin.
The step of method is:
(1) 1.0g nano hydrotalcite, 1.0～5.0g nano-calcium carbonate are joined in the 10～50g deionized water that contains 0.1～0.5g dispersion agent, at 20～100 ℃ of ultrasonic down or high speed shear dispersion 10～60min, obtain nano hydrotalcite and nano-calcium carbonate composite dispersion liquid;
(2) above nano hydrotalcite and nano-calcium carbonate composite dispersion liquid, 0.05～0.50g initiator, 0.1～0.5g dispersion agent, 100g vinylchlorid, 100～250g deionized water are joined in the polymeric kettle, after at room temperature stirring 10～60min, be warming up to 45～65 ℃ of polymerizations, be polymerized to system pressure decline 0.5～2.5kg/cm
2The time, finish polymerization, remove reacted vinyl chloride, discharging, filtration, drying obtain nano hydrotalcite and nano calcium carbonate composite modified polyvinyl chloride (PVC) RESINS.
Described nano hydrotalcite is the nano hydrotalcite of Zinic stearas surface modification.Nano-calcium carbonate is the nano-calcium carbonate of stearic acid surface modification.Initiator is one or both the mixture in azo class, the superoxide compounds.Dispersion agent is one or both the mixture in polyvinyl alcohol, the ether of cellulose.
Combining nano hydrotalcite of the present invention to the thermally-stabilised of PVC and press down the cigarette effect and nanoparticle to the impact-resistant modified effect of PVC, can obtain the PVC nanocomposite that thermostability and shock strength improve, the burning smoke density reduces; By implementing the pre-dispersed and in-situ suspension polymerization of nano hydrotalcite and nano-calcium carbonate, effectively reduce the reunion degree of nano hydrotalcite and nano-calcium carbonate, make them in the PVC matrix, reach dispersion comparatively uniformly.
Embodiment
It is Mg that the present invention selects molecular formula for use
0.667Al
0.333(OH)
2(CO
3)
22H
2O, primary particle particle diameter are less than the commercialization nano hydrotalcite of 100nm, Zinic stearas surface modification.The primary particle particle diameter of the nano-calcium carbonate that adopts is less than 100nm, and the surface adopts stearic acid to handle.
It is pre-dispersed that nano hydrotalcite and nano-calcium carbonate carry out water earlier, being about to a certain proportion of nano hydrotalcite and nano-calcium carbonate joins and contains suspension polymerization of VC with in the aqueous solution of dispersion agent, under high speed shear or ultrasonication, under the design temperature between 20～100 ℃, carry out pre-dispersed.Because the nanoparticle coacervate is partly dissociated, the dispersed particle median size reaches about 100nm, and in the colloid provide protection of dispersion agent, nano hydrotalcite that obtains and nano-calcium carbonate composite dispersion liquid have certain stability in storage.
The present invention adopts suspension polymerization to prepare the preparation of nano hydrotalcite and nano calcium carbonate composite modified polyvinyl chloride resin.Dispersion liquid, initiator, dispersion agent, deionized water and the vinylchlorid of above-mentioned nano hydrotalcite and nano-calcium carbonate are joined in the reactor, at room temperature reaction mass is stirred 10～60min, the intensification polymerization is reacted to system pressure decline 0.5～2.5kg/cm
2The time finish reaction, remove unreacted monomer, discharging, filtration, drying and obtain nano hydrotalcite and nano calcium carbonate composite modified polyvinyl chloride resin.
Polymerization can be selected chloroethylene polymerization oil-soluble initiator commonly used for use, as azo-initiators such as Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), and peroxide initiators such as peroxidation two acyl classes, peroxyesters, peroxy dicarbonates.As required, also can adopt two or more similar or non-similar initiator compound initiator system.
Suspension polymerization of VC dispersion agent commonly used is adopted in polymerization, comprises the dispersion agents such as polyvinyl alcohol of various cellulose etherses, different alcoholysis degrees.
The water oil quality is than between 1.2～2.5 during polymerization.Polymerization temperature is between 45～65 ℃.
Adopt that the total content of nano hydrotalcite and nano-calcium carbonate can calculate according to feed intake nano hydrotalcite and nano-calcium carbonate/vinylchlorid mass ratio and actual polymerisation conversion (weighting method mensuration) in nano hydrotalcite that above polymerization process obtains and the nano calcium carbonate composite modified polyvinyl chloride resin.The thermostability of PVC compound resin is tested by the congo red method of standard GB 2917-82 regulation.
PVC compound resin and organotin, epoxy soybean oil and the stearic acid of different nano hydrotalcites and nano-calcium carbonate calcium contents were pressed 100: 3.5: 1.5: 0.5 mixed.Under 175 ℃, use mixing about 8 minutes of twin-roll plastic mixing mill.With the compacting 10 minutes under the hydropress of 180 ℃ and 150MPa of the mixture that obtains, cooling obtains nano hydrotalcite and nano calcium carbonate composite modified PVC material test piece.The smoke density of modified PVC matrix material is measured by ASTM E662-95 standard.
Nano hydrotalcite and nano-calcium carbonate are stated in compound resin and the fabricated product in topic and are uniformly dispersed, and make compound resin have good thermostability, and its thermostability obviously is better than pure polyvinyl chloride resin.Simultaneously, the smoke density of being stated the PVC goods of compound resin processing by topic is significantly less than pure PVC, and therefore, topic is stated the production that the PVC/ nano hydrotalcite composite resin can be used for various PVC goods, especially electrical equipment, electric wire and building materials.
Embodiment 1
With 1.0g primary particle particle diameter is that the nano hydrotalcite (Dalian Fu Meida novel material company limited) of 20～60nm, nano-calcium carbonate, the 0.1g polyvinyl alcohol that 1.0g primary particle particle diameter is 40～80nm join in the 10g deionized water, at 20 ℃ of following ultra-sonic dispersion 30min, obtain the dispersion liquid of nano hydrotalcite and nano-calcium carbonate.
Above-mentioned dispersion liquid, 100g vinylchlorid, 0.15g peroxy dicarbonate ethylhexyl, 0.1g polyvinyl alcohol, 0.1g Vltra tears and 150g deionized water are joined in the reactor, after stirring 30min under the room temperature, be warming up to 57 ℃ of beginning polymerizations, be polymerized to system pressure decline 1.5kg/cm
2The time, cooling removes unreacted monomer, and discharging, filtration, drying obtain 83.5g nano hydrotalcite and nano calcium carbonate composite modified polyvinyl chloride resin.
Embodiment 2
With 1.0g primary particle particle diameter is that 20～60nm nano hydrotalcite (Dalian Fu Meida novel material company limited), 2.0g primary particle particle diameter are that 40～80nm nano-calcium carbonate, 0.2g polyvinyl alcohol join in the 20g deionized water, at 50 ℃ of following ultra-sonic dispersion 10min, obtain the dispersion liquid of nano hydrotalcite and nano-calcium carbonate.
Above-mentioned dispersion liquid, 100g vinylchlorid, 0.15g peroxy dicarbonate ethylhexyl, 0.1g polyvinyl alcohol, 0.1g Vltra tears and 150g deionized water are joined in the reactor, after stirring 30min under the room temperature, be warming up to 57 ℃ of beginning polymerizations, be polymerized to system pressure decline 1.5kg/cm
2The time, cooling removes unreacted monomer, and discharging, filtration, drying obtain 83.0g nano hydrotalcite and nano calcium carbonate composite modified polyvinyl chloride resin.
Embodiment 3
With 1.0g primary particle particle diameter is that 20～60nm nano hydrotalcite (Dalian Fu Meida novel material company limited), 3.0g primary particle particle diameter are that 40～80nm nano-calcium carbonate, 0.3g polyvinyl alcohol join in the 20g deionized water, at 50 ℃ of following ultra-sonic dispersion 30min, obtain the dispersion liquid of nano hydrotalcite and nano-calcium carbonate.
Above-mentioned dispersion liquid, 100g vinylchlorid, 0.15g peroxy dicarbonate ethylhexyl, 0.1g Vltra tears and 150g deionized water are joined in the reactor, after stirring 30min under the room temperature, be warming up to 57 ℃ of beginning polymerizations, be polymerized to system pressure decline 1.5kg/cm
2The time, cooling removes unreacted monomer, and discharging, filtration, drying obtain 82.4g nano hydrotalcite and nano calcium carbonate composite modified polyvinyl chloride resin.
Embodiment 4
With 1.0g primary particle particle diameter is that 20～60nm nano hydrotalcite (Dalian Fu Meida novel material company limited), 4.0g primary particle particle diameter are that 40～80nm nano-calcium carbonate, 0.4g polyvinyl alcohol join in the 20g deionized water, disperse 30min 50 ℃ of following high speed shear, obtain the dispersion liquid of nano hydrotalcite and nano-calcium carbonate.
Above-mentioned dispersion liquid, 100g vinylchlorid, 0.15g peroxy dicarbonate ethylhexyl, 0.1g Vltra tears and 150g deionized water are joined in the reactor, after stirring 30min under the room temperature, be warming up to 57 ℃ of beginning polymerizations, be polymerized to system pressure decline 1.5kg/cm
2The time, cooling removes unreacted monomer, and discharging, filtration, drying obtain 83.0g nano hydrotalcite and nano calcium carbonate composite modified polyvinyl chloride resin.
Embodiment 5
With 1.0g primary particle particle diameter is that 20～60nm nano hydrotalcite (Dalian Fu Meida novel material company limited), 5.0g primary particle particle diameter are that 40～80nm nano-calcium carbonate, 0.5g polyvinyl alcohol join in the 50g deionized water, disperse 60min 50 ℃ of following high speed shear, obtain the dispersion liquid of nano hydrotalcite and nano-calcium carbonate.
Above-mentioned dispersion liquid, 100g vinylchlorid, 0.15g peroxy dicarbonate ethylhexyl, 0.1g Vltra tears and 150g deionized water are joined in the reactor, after stirring 30min under the room temperature, be warming up to 57 ℃ of beginning polymerizations, be polymerized to system pressure decline 1.5kg/cm
2The time, cooling removes unreacted monomer, and discharging, filtration, drying obtain 82.0g nano hydrotalcite and nano calcium carbonate composite modified polyvinyl chloride resin.
Embodiment 6
With 1.0g primary particle particle diameter is that 20～60nm nano hydrotalcite (Dalian Fu Meida novel material company limited), 2.0g primary particle particle diameter are that 40～80nm nano-calcium carbonate, 0.2g polyvinyl alcohol join in the 20g deionized water, disperse 10min 100 ℃ of following high speed shear, obtain the dispersion liquid of nano hydrotalcite and nano-calcium carbonate.
Above-mentioned dispersion liquid, 100g vinylchlorid, 0.5g di-cyclohexylperoxy dicarbonate, 0.1g Vltra tears and 200g deionized water are joined in the reactor, after stirring 30min under the room temperature, be warming up to 45 ℃ of beginning polymerizations, be polymerized to system pressure decline 0.5kg/cm
2The time, cooling removes unreacted monomer, and discharging, filtration, drying obtain 80.0g nano hydrotalcite and nano calcium carbonate composite modified polyvinyl chloride resin.
Embodiment 7
With 1.0g primary particle particle diameter is that 20～60nm nano hydrotalcite (Dalian Fu Meida novel material company limited), 2.0g primary particle particle diameter are that 40～80nm nano-calcium carbonate, 0.2g polyvinyl alcohol join in the 20g deionized water, disperse 30min 50 ℃ of following high speed shear, obtain the dispersion liquid of nano hydrotalcite and nano-calcium carbonate.
Above-mentioned dispersion liquid, 100g vinylchlorid, 0.50g 2,2'-Azobis(2,4-dimethylvaleronitrile), 0.2g Vltra tears and 250g deionized water are joined in the reactor, behind the stirring 60min, be warming up to 60 ℃ of beginning polymerizations under the room temperature, be polymerized to system pressure decline 2.0kg/cm
2The time, cooling removes unreacted monomer, and discharging, filtration, drying obtain 83.1g nano hydrotalcite and nano calcium carbonate composite modified polyvinyl chloride resin.
Embodiment 8
With 1.0g primary particle particle diameter is that 20～60nm nano hydrotalcite (Dalian Fu Meida novel material company limited), 2.0g primary particle particle diameter are that 40～80nm nano-calcium carbonate, 0.1g polyvinyl alcohol join in the 20g deionized water, disperse 10min 100 ℃ of following high speed shear, obtain the dispersion liquid of nano hydrotalcite and nano-calcium carbonate.
Above-mentioned dispersion liquid, 100g vinylchlorid, 0.05g Diisopropyl azodicarboxylate, 0.05g peroxy dicarbonate ethylhexyl, 0.1g Vltra tears and 200g deionized water are joined in the reactor, after stirring 15min under the room temperature, be warming up to 62 ℃ of beginning polymerizations, be polymerized to system pressure decline 2.5kg/cm
2The time, cooling removes unreacted monomer, and discharging, filtration, drying obtain 83.7g nano hydrotalcite and nano calcium carbonate composite modified polyvinyl chloride resin.
Comparative example 1
With 200g deionized water, 0.15g polyvinyl alcohol, 0.15g Vltra tears, 0.15g peroxy dicarbonate ethylhexyl and 100g vinylchlorid join in the reactor, after stirring 30min under the room temperature, be warming up to 57 ℃ of beginning polymerizations, being polymerized to system pressure is 6.0kg/cm
2The time, cooling removes unreacted monomer, and discharging, filtration, drying obtain the 82.0gPVC resin.
The nano hydrotalcite and the nano hydrotalcite and the nano-calcium carbonate total content of nano calcium carbonate composite modified polyvinyl chloride resin, the heat-stable time that adopts Congo red variable color method mensuration, processed sample burning smoke density and the notched Izod impact strength that adopt above embodiment to obtain are as shown in table 1.As seen, with nano hydrotalcite and nono calcium carbonate modified PVC, the resin heat-stable time significantly improves, and the maximum smoke density that burns descends more than 38%; When the nano hydrotalcite consumption constant, and the nano-calcium carbonate consumption is when increasing, heat-stable time improves and the smoke density fall slightly increases, and the increase of notched Izod impact strength is comparatively obvious, illustrated thermally-stabilised and what press down the cigarette effect mainly is nano hydrotalcite, and the effect that improves the PVC shock strength has been played in the adding of nano-calcium carbonate, nano hydrotalcite and nono calcium carbonate modified PVC have good thermally-stabilised, press down cigarette and shock strength.
The heat-stable time of table 1 PVC and PVC/ nano hydrotalcite composite resin and burning smoke density
| Numbering | Nano hydrotalcite and nano-calcium carbonate total content (wt%) | Heat-stable time (min) | Maximum smoke density burns | Notched Izod impact strength (kJ/m 2) |
| Comparative example 1 | 0 | 2 | 750 | 2.31 |
| Embodiment 1 | 2.40 | 15.0 | 465 | 2.99 |
| Embodiment 2 | 3.61 | 15.5 | 454 | 3.54 |
| Embodiment 3 | 4.85 | 16.8 | 424 | 4.61 |
| Embodiment 4 | 6.02 | 19.5 | 413 | 5.12 |
| Embodiment 5 | 7.32 | 21.2 | 401 | 4.85 |
| Embodiment 6 | 3.75 | 16.0 | 435 | 3.60 |
| Embodiment 7 | 3.61 | 15.8 | 441 | 3.48 |
| Embodiment 8 | 3.58 | 15.6 | 435 | 3.39 |
Claims (5)
1. the preparation method of nano hydrotalcite and nano calcium carbonate composite modified polyvinyl chloride resin is characterized in that the step of method is:
(1) 1.0g nano hydrotalcite, 1.0～5.0g nano-calcium carbonate are joined in the 10～50g deionized water that contains 0.1～0.5g dispersion agent, at 20～100 ℃ of ultrasonic down or high speed shear dispersion 10～60min, obtain nano hydrotalcite and nano-calcium carbonate composite dispersion liquid;
(2) above nano hydrotalcite and nano-calcium carbonate composite dispersion liquid, 0.05～0.50g initiator, 0.1～0.5g dispersion agent, 100g vinylchlorid, 100～250g deionized water are joined in the polymeric kettle, after at room temperature stirring 10～60min, be warming up to 45～65 ℃ of polymerizations, be polymerized to system pressure decline 0.5～2.5kg/cm
2The time, finish polymerization, remove reacted vinyl chloride, discharging, filtration, drying obtain nano hydrotalcite and nano calcium carbonate composite modified polyvinyl chloride (PVC) RESINS.
2. the preparation method of a kind of nano hydrotalcite according to claim 1 and nano calcium carbonate composite modified polyvinyl chloride resin is characterized in that described nano hydrotalcite is the nano hydrotalcite of Zinic stearas surface modification.
3. the preparation method of a kind of nano hydrotalcite according to claim 1 and nano calcium carbonate composite modified polyvinyl chloride resin is characterized in that described nano-calcium carbonate is the nano-calcium carbonate of stearic acid surface modification.
4. the preparation method of a kind of nano hydrotalcite according to claim 1 and nano calcium carbonate composite modified polyvinyl chloride resin is characterized in that described initiator is one or both the mixture in azo class, the superoxide compounds.
5. the preparation method of a kind of nano hydrotalcite according to claim 1 and nano calcium carbonate composite modified polyvinyl chloride resin is characterized in that described dispersion agent is one or both the mixture in polyvinyl alcohol, the ether of cellulose.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103242608A (en) * | 2013-06-03 | 2013-08-14 | 鸡东县华鑫塑料制品有限公司 | Polymer energy-saving environment-friendly rare earth composite PVC (Polyvinyl Chloride) resin special material |
| CN104177524A (en) * | 2014-08-14 | 2014-12-03 | 杭州华纳化工有限公司 | Preparation method of graphene/nano calcium carbonate/vinyl chloride ternary copolymer resin by in-situ suspension polymerization |
| CN104592671A (en) * | 2014-08-05 | 2015-05-06 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | Nanometer calcium carbonate-polyvinyl chloride composite resin preparation method |
| CN105418813A (en) * | 2015-12-19 | 2016-03-23 | 仇颖超 | Preparation method of functional nano calcium carbonate reinforced polyvinyl chloride resin |
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2007
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242608A (en) * | 2013-06-03 | 2013-08-14 | 鸡东县华鑫塑料制品有限公司 | Polymer energy-saving environment-friendly rare earth composite PVC (Polyvinyl Chloride) resin special material |
| CN103242608B (en) * | 2013-06-03 | 2015-04-08 | 鸡东县华鑫塑料制品有限公司 | Polymer energy-saving environment-friendly rare earth composite PVC (Polyvinyl Chloride) resin special material |
| CN104592671A (en) * | 2014-08-05 | 2015-05-06 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | Nanometer calcium carbonate-polyvinyl chloride composite resin preparation method |
| CN104592671B (en) * | 2014-08-05 | 2017-09-29 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | A kind of preparation method of nano-calcium carbonate polychloroethylene compound resin |
| CN104177524A (en) * | 2014-08-14 | 2014-12-03 | 杭州华纳化工有限公司 | Preparation method of graphene/nano calcium carbonate/vinyl chloride ternary copolymer resin by in-situ suspension polymerization |
| CN104177524B (en) * | 2014-08-14 | 2016-01-27 | 杭州华纳化工有限公司 | A kind of graphene/nanometer calcium carbonate/vinylchlorid terpolymer resin in-situ suspension polymerization method |
| CN105418813A (en) * | 2015-12-19 | 2016-03-23 | 仇颖超 | Preparation method of functional nano calcium carbonate reinforced polyvinyl chloride resin |
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