CN101759834A - Polyvinyl chloride processing plasticizing modifier, preparation method and application thereof - Google Patents
Polyvinyl chloride processing plasticizing modifier, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a polyvinyl chloride processing plasticizing modifier, which is characterized in that the modifier is a high-molecular polymer of 100 parts by weight, which is obtained by using (in parts by weight) 0-100 parts of alkyl methacrylate, 0-40 parts of alkyl acrylate, 0-85 parts of styrene monomer and 0-35 parts of acrylonitrile monomer and making the components undergo the process of monomer mixture copolymerization and the intrinsic viscosity of which is greater than 13.0 and is less than or equal to 16.0.The preparation method includes the following steps: adding 100-200 parts of water, monomer combination, surfactant and free radical initiator into a reactor, stirring and warming up to 50 DEG C, controlling the reaction temperature below 50 DEG C-60 DEG C, reacting for 15-30 hours, so as to obtain polymer emulsion, then drying and obtaining the high-molecular polymer. When the high-molecular polymer is used as the polyvinyl chloride processing plasticizing modifier, the adding weight ratio is 0.1% to 15% of the weight of polyvinyl chloride.
Description
Technical field
The present invention relates to a kind of polyvinyl chloride processing and use the modified additive field, relate in particular to a kind of polyvinyl chloride processing plasticizing modifier, preparation method and application thereof.
Background technology
Polyvinyl chloride (PVC) is a kind of universal thermoplastics of excellent property, is one of plastics variety of China's output maximum.Polyvinyl chloride to shape performance relatively poor, must add the processing characteristics improving agent to improve its plasticizing processing characteristics, esters of acrylic acid processing characteristics properties-correcting agent is a kind of in three kinds of properties-correcting agent generally adopting at present of China, but the limiting viscosity of all at present esters of acrylic acid processing characteristics properties-correcting agent is generally less than 6.0.
The contriver finds in experiment, modification performance and its inherent viscosity of polyvinyl chloride processing plasticizing modifier are closely related, inherent viscosity is big more, polyvinyl chloride processing characteristics through modification is good more, and the effective means that improves the processing characteristics of polyvinyl chloride (PVC) Compound is to use the higher properties-correcting agent of limiting viscosity.
When making esters of acrylic acid polyvinyl chloride processing characteristics properties-correcting agent, the polyreaction operation is that substep or batch-wise add, and to prevent reaction aggravation under material is too much or temperature of reaction the is too high situation, causes the damage of reactor or reaction accident to take place.The PVC modified limiting viscosity of using processing aid of limiting viscosity maximum is all below 13.0 now, and the processing characteristics of the polyvinyl chloride after modification is all not ideal enough.
Summary of the invention
Technical problem to be solved by this invention provides a kind of limiting viscosity greater than 13.0 and smaller or equal to 16.0 polyvinyl chloride processing plasticizing modifier, preparation method and application thereof.
For solving the problems of the technologies described above, technical scheme of the present invention is:
A kind of polyvinyl chloride processing plasticizing modifier, the weight part that it is made up of the acrylonitrile monemer of the styrene monomer of the alkyl methacrylate of 0～100 weight part, 0～40 parts by weight of acrylic alkyl ester, 0～85 weight part and 0～35 weight part are the limiting viscosity that obtains of 100 monomer mixture copolymerization greater than 13.0 and smaller or equal to 16.0 high molecular polymer.
Preferred polyvinyl chloride processing plasticizing modifier, described alkyl methacrylate is 0～80 weight part, described alkyl acrylate is 0～40 weight part, and described styrene monomer is 0～85 weight part, and described vinyl cyanide monomer is 0～35 weight part.
Limiting viscosity is greater than 13.0 and prepared by following method smaller or equal to 16.0 high molecular polymer:
Water with 100～200 weight parts, alkyl methacrylate by 0～100 weight part, 0～40 parts by weight of acrylic alkyl ester, the weight part that the vinyl cyanide monomer of the styrene monomer of 0～85 weight part and 0～35 weight part is formed is 100 composition, 0.5 the radical initiator of the tensio-active agent of～4.0 weight parts and 0.005～0.5 weight part joins in the reactor simultaneously, under 50～500 rev/mins stirring velocity, be warming up to 50 ℃, temperature of reaction is controlled at below 50～60 ℃, reacted 15～30 hours, obtain polymer emulsion, drying obtains this high molecular polymer again.
Preferably, limiting viscosity is greater than 13.0 and prepared by following method smaller or equal to 16.0 high molecular polymer:
Water with 100～200 weight parts, alkyl methacrylate by 0～80 weight part, 0～40 parts by weight of acrylic alkyl ester, the weight part that the vinyl cyanide monomer of the styrene monomer of 0～85 weight part and 0～35 weight part is formed is 100 composition, 0.5 the radical initiator of the tensio-active agent of～4.0 weight parts and 0.005～0.5 weight part joins in the reactor simultaneously, under 50～500 rev/mins stirring velocity, be warming up to 50 ℃, temperature of reaction is controlled at below 50 ℃, reacted 15～30 hours, obtain polymer emulsion, drying obtains this high molecular polymer again.
The carbonatoms of the alkyl of described alkyl methacrylate is 1～8, the carbonatoms of the alkyl of described alkyl acrylate is 2～8, described styrene monomer is vinylbenzene or α～vinyl toluene, and described vinyl cyanide monomer is vinyl cyanide or methacrylonitrile.
Described tensio-active agent is Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, sodium lauryl sulphate, sodium stearate or dodecyl sulphate potassium, and described radical initiator is Potassium Persulphate or ammonium persulphate.
The viscosity number of described limiting viscosity for adopting dark type viscometer to measure.
The application of polyvinyl chloride processing plasticizing modifier, the interpolation weight ratio that it is characterized in that this polyvinyl chloride processing plasticizing modifier is 0.1%～15% of a polyvinyl chloride weight.
The limiting viscosity that the inventor chances on polyvinyl chloride processing characteristics properties-correcting agent is subjected to the influence of polymeric reaction condition of properties-correcting agent very big, particularly the feed way of the starting monomer of multipolymer, reaction times and temperature of reaction.The disposable reinforced limiting viscosity maximum that obtains polymkeric substance, reinforced number of times is many more, and viscosity is more little; Control reaction temperature is low more, and its limiting viscosity is big more; Reaction times is long more, and then limiting viscosity is big more.Carry out polyreaction with the monomer of above-mentioned composition proportioning or monomer mixture and tensio-active agent, the disposable input simultaneously of initiator, meet under the condition of above-mentioned requirements at controlled temperature and reaction times, can obtain the limiting viscosity coefficient greater than 13.0 modifier polymer.But those skilled in the art generally believes that this polyreaction is thermopositive reaction, and speed of response is aggravated along with increasing of temperature of reaction, must react feed rate and temperature of reaction by strict controlled polymerization, prevent that sudden and violent poly-reaction is with the safe operation of assurance polymerization reactor and operator's personnel safety, prevent the generation of accident, therefore can not disposable various materials be joined in the reactor.If all materials of disposable adding not only can not get polymkeric substance, but also can cause danger.The contriver has overcome those skilled in the art cognitive defect, with the disposable input reactor of all monomer components, accelerating to control whole polymeric reaction temperature condition under the radiating rate situation of reactor, obtaining limiting viscosity greater than 13.0 polyvinyl chloride processing plasticizing modifier.
The method that the present invention measures limiting viscosity is: earlier processing plasticizing modifier is put into 65 ℃ of thermostat containers and keep 10h, cooling back with ten thousand/ the accurate weighing 0.072g of balance put into the 25ml volumetric flask, the trichloromethane that adds then about 20 milliliters makes it dissolving, placed 24 hours, after treating all dissolvings, put into 25 ± 0.1 ℃ Water Tank with Temp.-controlled, constant temperature 15min, be diluted to the 25ml scale with trichloromethane again, to be determined with No. 3 sand core funnels filtration backs, measure its viscosity with dark type viscometer then, measure the viscosity of trichloromethane simultaneously.
Method of calculation
η
r＝t/t
0????????????η
sp＝η
r-1
T is that modifier solution is flowed through the time capillaceous t in the formula
0Be that the solution trichloromethane is flowed through the same time capillaceous, c is the concentration (g/100ml) of solution
η
rBe relative viscosity, η
SpBe specific viscosity, η is a limiting viscosity.
Owing to adopted technique scheme, beneficial effect of the present invention is, the contriver has broken through understanding limitation and the mistaken ideas in the industry field, and by control reaction temperature and reaction times, under the situation of the radiating rate of accelerating reactor, obtained the limiting viscosity coefficient greater than 13.0 and smaller or equal to the properties-correcting agent of 16.0 high molecular polymer, and adopt this high molecular polymer as improve the polyvinyl chloride soffening can properties-correcting agent and the preparation method of this properties-correcting agent is provided, this properties-correcting agent can effectively improve the smooth finish of polyvinyl chloride rheology piece, improves the plasticizing capacity of polyvinyl chloride.This properties-correcting agent can be widely used in the improvement of the processing characteristics of igelite or polyvinyl chloride composite materials.
Embodiment
The present invention is further illustrated to use specific embodiment and comparative example below, and embodiment 1 and comparative example 1-2 adopt same monomer component to form, and controls identical reaction times and temperature to increase the comparability of test-results.But the present invention is not limited to these embodiment.
Embodiment 1
With the methyl methacrylate of the water of 150 weight parts, 96 weight parts, 4 parts by weight of acrylic butyl esters, the sodium lauryl sulphate of 2 weight parts, the disposable reactor of putting into of Potassium Persulphate of 0.2 weight part, under 200 rev/mins mixing speed, be warming up to 50 ℃, and temperature remained on below 60 ℃ reaction 15 hours, obtain the emulsion of acrylate copolymer, obtain limiting viscosity after the drying and be 13.5 acrylic acid esters co-polymer.
Embodiment 2
With the methyl methacrylate of the water of 160 weight parts, 96 weight parts, 4 parts by weight of acrylic butyl esters, the sodium lauryl sulphate of 2 weight parts, the disposable reactor of putting into of Potassium Persulphate of 0.2 weight part, under 200 rev/mins mixing speed, be warming up to 50 ℃, and temperature remained on below 55 ℃ reaction 15 hours, obtain the emulsion of acrylate copolymer, obtain limiting viscosity after the drying and be 14.0 acrylic acid esters co-polymer.
Embodiment 3
With embodiment 2, just temperature of reaction is controlled at below 50 ℃.
Comparative example 1 is with embodiment 1, just join the methyl methacrylate of 96 weight parts and the mixture of 4 parts by weight of acrylic butyl esters in the reactor at twice, the order that adds is to add the second endorsement body in the intact back of first monomer reaction, and temperature of reaction is controlled at below 70 ℃.
Comparative example 2 is with embodiment 1, just the mixture of the methyl methacrylate of 90 weight parts and 10 parts by weight of acrylic butyl esters is divided and join in the reactor for three times, the order that adds is to add the second endorsement body in the intact back of first monomer reaction, the 3rd endorsement body adds after second batch reaction is finished, and temperature of reaction is controlled at below 70 ℃.
Test and appraisal to polyvinyl chloride processing characteristics after the modification: can pass through the highest moment of torsion and balancing torque that RM-200 torque rheometer (manufacturing of Haast company of Harbin University of Science and Technology) is measured the polyvinyl chloride after the processing plasticizing modifier modification of different qualities viscosity, with the difference of processing plasticizing performance relatively, the highest moment of torsion the and processing characteristics of the polyvinyl chloride of high balancing torque is best.The condition of test and appraisal is rotor speed 35rpm, 165 ℃ of design temperatures.Estimating the weight part prescription is: 100 parts of polyvinyl chloride, 5 parts in lime carbonate, 3 parts of disalts, 0.15 part in chlorinatedpolyethylene wax, 0.2 part of stearic acid, 9 parts of chlorinatedpolyethylenees, 1.5 parts of processing plasticizing modifiers provided by the invention, this 0.7 part of stearic acid, 1.0 parts of lead stearates.
With the polyvinyl chloride of RM-200 torque rheometer test through the above-mentioned prescription of the processing plasticizing modifier modification of various different qualities viscosity, its comparing result sees Table 1.
Table 1 processing plasticizing modifier influences the contrast of situation to polyvinyl chloride rheology piece smooth finish
| Inherent viscosity | The highest moment of torsion (Nm) | Balancing torque (Nm) | Rheology piece smooth finish | |
| Embodiment 1 | ??13.5 | ??36.9 | ??34.3 | ??00000 |
| Inherent viscosity | The highest moment of torsion (Nm) | Balancing torque (Nm) | Rheology piece smooth finish | |
| Embodiment 2 | ??14.1 | ??37.6 | ??35.2 | ??0000 |
| Embodiment 3 | ??15.0 | ??38.3 | ??36.1 | ??0000 |
| Comparative example 1 | ??9.3 | ??34.7 | ??32.5 | ??00 |
| Comparative example 2 | ??7.8 | ??33.5 | ??30.8 | ??0 |
The relation of polyvinyl chloride rheology piece smooth finish is as follows in the table:
Limiting viscosity is big more as can be seen from Table 1, and the polyvinyl chloride balancing torque after the modification is high more high more with the highest moment of torsion, and the smooth finish of rheology piece is good more, thereby the plasticizing effect of the polyvinyl chloride after the proof modification is good more.If it is in reaction, add the inherent viscosity that end-capping reagent also can influence prepared plasticizing modifier, but the modified effect of plasticizing modifier is only relevant with the size of its inherent viscosity, irrelevant with other factor that influences the polymerizable molecular amount.
Embodiment 4
With the water of 120 weight parts, the methyl methacrylate of 50 weight parts, the styrene monomer of 30 weight parts, the acrylonitrile monemer of 20 weight parts, the Sodium dodecylbenzene sulfonate of 3.0 weight parts, the disposable reactor of putting into of Potassium Persulphate of 0.36 weight part, under 500 rev/mins mixing speed, be warming up to 50 ℃, and temperature remained on below 52 ℃ reaction 20 hours, obtain the emulsion of multipolymer, obtain limiting viscosity after the drying and be 14.8 high-molecular copolymer.
Embodiment 5
With the water of 100 weight parts, the methyl methacrylate of 25 weight parts, the vinylbenzene of 15 weight parts, the acrylonitrile monemer of 10 weight parts, the styrene monomer of 50 weight parts, the dodecyl sulphate potassium of 1.5 weight parts, the disposable reactor of putting into of ammonium persulphate of 0.2 weight part, under 50 rev/mins mixing speed, be warming up to 50 ℃, and temperature remained on below 57 ℃ reaction 20 hours, obtain the emulsion of multipolymer, obtain limiting viscosity after the drying and be 13.7 acrylic acid esters co-polymer.
Embodiment 6
With the water of 130 weight parts, the methyl methacrylate of 50 weight parts, the styrene monomer of 30 weight parts, the acrylonitrile monemer of 20 weight parts, the sodium laurylsulfonate of 3.6 weight parts, the disposable reactor of putting into of Potassium Persulphate of 0.42 weight part, under 300 rev/mins mixing speed, be warming up to 50 ℃, and temperature remained on below 48 ℃ reaction 25 hours, obtain the emulsion of multipolymer, obtain limiting viscosity after the drying and be 15.5 high-molecular copolymer.
The plasticizing modifier that obtains with embodiment 4,5 and 6 carries out modified test to polyvinyl chloride, test recipe and plasticizing assessment method are with embodiment 1 and 2, test-results shows, the plasticizing modifier that inherent viscosity is big more is obvious more to the plasticizing improvement of polyvinyl chloride, but the modified effect of above-mentioned three kinds of plasticizing modifiers is all apparently higher than the existing modified effect of forming identical properties-correcting agent.
Embodiment 7
With the Octyl methacrylate of the water of 130 weight parts, 24 weight parts, 48 parts by weight of acrylic monooctyl esters, the styrene monomer of 6 weight parts, the acrylonitrile monemer of 22 weight parts, the sodium stearate of 3.3 weight parts, the disposable reactor of putting into of Potassium Persulphate of 0.36 weight part, under 100 rev/mins mixing speed, be warming up to 50 ℃, and temperature remained on below 55 ℃ reaction 25 hours, obtain the emulsion of multipolymer, obtain limiting viscosity after the drying and be 14.2 acrylic acid esters co-polymer.
Embodiment 8
With the styrene monomer of the water of 180 weight parts, 15 parts by weight of acrylic ester, 30 weight parts, the methyl methacrylate of 55 weight parts, the sodium stearate of 4.0 weight parts, the disposable reactor of putting into of ammonium persulphate of 0.50 weight part, under 50 rev/mins mixing speed, be warming up to 50 ℃, and temperature remained on below 54 ℃ reaction 23 hours, obtain the emulsion of multipolymer, obtain limiting viscosity after the drying and be 14.7 acrylic acid esters co-polymer.
Embodiment 9
With the methacrylic nitrile monomer of the methacrylic acid of the water of 160 weight parts, 80 weight parts ester, 20 weight parts, the sodium lauryl sulphate of 4.0 weight parts, the disposable reactor of putting into of Potassium Persulphate of 0.45 weight part, under 240 rev/mins mixing speed, be warming up to 50 ℃, and temperature remained on below 60 ℃ reaction 20 hours, obtain the emulsion of multipolymer, obtain limiting viscosity after the drying and be 13.7 acrylic acid esters co-polymer.
Embodiment 10
With the water of 140 weight parts, the styrene monomer of 70 weight parts, the acrylonitrile monemer of 30 weight parts, the dodecyl sulphate potassium of 4.0 weight parts, the disposable reactor of putting into of Potassium Persulphate of 0.36 weight part, under 120 rev/mins mixing speed, be warming up to 50 ℃, and temperature remained on below 55 ℃ reaction 25 hours, obtain the emulsion of multipolymer, obtain limiting viscosity after the drying and be 14.2 acrylic acid esters co-polymer.
Embodiment 11
With the Jia Jibingxisuanyizhi of the water of 140 weight parts, 50 weight parts, 10 parts by weight of acrylic heptyl esters, the styrene monomer of 20 weight parts, the methacrylic nitrile monomer of 20 weight parts, the sodium stearate of 3.2 weight parts, the disposable reactor of putting into of Potassium Persulphate of 0.2 weight part, under 100 rev/mins mixing speed, be warming up to 50 ℃, and temperature remained on below 55 ℃ reaction 26 hours, obtain the emulsion of multipolymer, obtain limiting viscosity after the drying and be 13.8 acrylic acid esters co-polymer.
Embodiment 12
With the propyl methacrylate of the water of 150 weight parts, 60 weight parts, 10 parts by weight of acrylic monooctyl esters, the styrene monomer of 10 weight parts, the methacrylic nitrile monomer of 20 weight parts, the sodium laurylsulfonate of 2.8 weight parts, the disposable reactor of putting into of ammonium persulphate of 0.25 weight part, under 200 rev/mins mixing speed, be warming up to 50 ℃, and temperature remained on below 56 ℃ reaction 15 hours, obtain the emulsion of multipolymer, obtain limiting viscosity after the drying and be 13.8 acrylic acid esters co-polymer.
Embodiment 13
With the butyl methacrylate of the water of 140 weight parts, 80 weight parts, 5 parts by weight of acrylic pentyl esters, the styrene monomer of 5 weight parts, the acrylonitrile monemer of 10 weight parts, the dodecyl sulphate potassium of 2.5 weight parts, the disposable reactor of putting into of ammonium persulphate of 0.25 weight part, under 50 rev/mins mixing speed, be warming up to 50 ℃, and temperature remained on below 60 ℃ reaction 10 hours, obtain the emulsion of multipolymer, obtain limiting viscosity after the drying and be 13.5 acrylic acid esters co-polymer.
Embodiment 14
With the water of 100 weight parts, the methyl methacrylate of 80 weight parts, the styrene monomer of 20 weight parts, the sodium laurylsulfonate of 2.2 weight parts, the disposable reactor of putting into of Potassium Persulphate of 0.15 weight part, under 500 rev/mins mixing speed, be warming up to 50 ℃, and temperature remained on below 55 ℃ reaction 20 hours, obtain the emulsion of multipolymer, obtain limiting viscosity after the drying and be 14.2 acrylic acid esters co-polymer.
Claims (8)
1. polyvinyl chloride processing plasticizing modifier is characterized in that weight part that it is made up of the acrylonitrile monemer of the styrene monomer of the alkyl methacrylate of 0～100 weight part, 0～40 parts by weight of acrylic alkyl ester, 0～85 weight part and 0～35 weight part is the limiting viscosity that obtains of 100 monomer mixture copolymerization greater than 13.0 and smaller or equal to 16.0 high molecular polymer.
2. polyvinyl chloride processing plasticizing modifier as claimed in claim 1, it is characterized in that described alkyl methacrylate is 0～80 weight part, described alkyl acrylate is 0～40 weight part, described styrene monomer is 0～85 weight part, and described vinyl cyanide monomer is 0～35 weight part.
3. polyvinyl chloride processing plasticizing modifier as claimed in claim 1 is characterized in that limiting viscosity is greater than 13.0 and prepared by following method smaller or equal to 16.0 high molecular polymer:
Water with 100～200 weight parts, alkyl methacrylate by 0～100 weight part, 0～40 parts by weight of acrylic alkyl ester, the weight part that the vinyl cyanide monomer of the styrene monomer of 0～85 weight part and 0～35 weight part is formed is 100 composition, 0.5 the radical initiator of the tensio-active agent of～4.0 weight parts and 0.005～0.5 weight part joins in the reactor simultaneously, under 50～500 rev/mins stirring velocity, be warming up to 50 ℃, temperature of reaction is controlled at below 50～60 ℃, reacted 15～30 hours, obtain polymer emulsion, drying obtains this high molecular polymer again.
4. polyvinyl chloride processing plasticizing modifier as claimed in claim 2 is characterized in that limiting viscosity is greater than 13.0 and prepared by following method smaller or equal to 16.0 high molecular polymer:
Water with 100～200 weight parts, alkyl methacrylate by 0～80 weight part, 0～40 parts by weight of acrylic alkyl ester, the weight part that the vinyl cyanide monomer of the styrene monomer of 0～85 weight part and 0～35 weight part is formed is 100 composition, 0.5 the radical initiator of the tensio-active agent of～4.0 weight parts and 0.005～0.5 weight part joins in the reactor simultaneously, under 50～500 rev/mins stirring velocity, be warming up to 50 ℃, temperature of reaction is controlled at below 50 ℃, reacted 15～30 hours, obtain polymer emulsion, drying obtains this high molecular polymer again.
5. polyvinyl chloride processing plasticizing modifier as claimed in claim 1 or 2, the carbonatoms that it is characterized in that the alkyl of described alkyl methacrylate is 1～8, the carbonatoms of the alkyl of described alkyl acrylate is 2～8, described styrene monomer is vinylbenzene or α～vinyl toluene, and described vinyl cyanide monomer is vinyl cyanide or methacrylonitrile.
6. as claim 3 or 4 described polyvinyl chloride processing plasticizing modifiers, it is characterized in that described tensio-active agent is Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, sodium lauryl sulphate, sodium stearate or dodecyl sulphate potassium, described radical initiator is Potassium Persulphate or ammonium persulphate.
7. polyvinyl chloride processing plasticizing modifier as claimed in claim 1 or 2 is characterized in that the viscosity number of described limiting viscosity for adopting dark type viscometer to measure.
8. the application of polyvinyl chloride processing plasticizing modifier as claimed in claim 1 or 2, the interpolation weight ratio that it is characterized in that this polyvinyl chloride processing plasticizing modifier is 0.1%～15% of a polyvinyl chloride weight.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181107A (en) * | 2011-04-01 | 2011-09-14 | 安徽玉发塑业有限公司 | Plasticized polyvinyl chloride pipe |
| CN109517297A (en) * | 2018-11-07 | 2019-03-26 | 山东日科化学股份有限公司 | Polychloroethylene section bar compound material, automatically cleaning polyvinyl chloride door-window section bar and preparation method thereof |
| CN109535310A (en) * | 2018-11-07 | 2019-03-29 | 山东日科化学股份有限公司 | Foaming control agent and preparation method, polyvinyl chloride composite material, polyvinyl-chloride foam material and its application |
-
2010
- 2010-01-08 CN CN201010011521A patent/CN101759834A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181107A (en) * | 2011-04-01 | 2011-09-14 | 安徽玉发塑业有限公司 | Plasticized polyvinyl chloride pipe |
| CN109517297A (en) * | 2018-11-07 | 2019-03-26 | 山东日科化学股份有限公司 | Polychloroethylene section bar compound material, automatically cleaning polyvinyl chloride door-window section bar and preparation method thereof |
| CN109535310A (en) * | 2018-11-07 | 2019-03-29 | 山东日科化学股份有限公司 | Foaming control agent and preparation method, polyvinyl chloride composite material, polyvinyl-chloride foam material and its application |
| CN109517297B (en) * | 2018-11-07 | 2021-06-04 | 山东日科化学股份有限公司 | Polyvinyl chloride profile composite material, self-cleaning polyvinyl chloride door and window profile and preparation method thereof |
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Open date: 20100630 |