CN115948007A - High-toughness and high-stability PVC (polyvinyl chloride) and preparation method thereof - Google Patents
High-toughness and high-stability PVC (polyvinyl chloride) and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000004800 polyvinyl chloride Substances 0.000 title description 78
- 229920000915 polyvinyl chloride Polymers 0.000 title description 77
- 239000000463 material Substances 0.000 claims abstract description 53
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003381 stabilizer Substances 0.000 claims abstract description 23
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 14
- 239000012745 toughening agent Substances 0.000 claims abstract description 13
- AJDTZVRPEPFODZ-PAMPIZDHSA-J [Sn+4].[O-]C(=O)\C=C/C([O-])=O.[O-]C(=O)\C=C/C([O-])=O Chemical compound [Sn+4].[O-]C(=O)\C=C/C([O-])=O.[O-]C(=O)\C=C/C([O-])=O AJDTZVRPEPFODZ-PAMPIZDHSA-J 0.000 claims abstract description 12
- 239000000945 filler Substances 0.000 claims abstract description 10
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 9
- 239000000314 lubricant Substances 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- 150000002688 maleic acid derivatives Chemical class 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- 239000012760 heat stabilizer Substances 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- -1 polyethylene Polymers 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000004709 Chlorinated polyethylene Substances 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 239000000779 smoke Substances 0.000 claims 1
- 229920003023 plastic Polymers 0.000 abstract description 4
- 239000004033 plastic Substances 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 11
- 238000000354 decomposition reaction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000003017 thermal stabilizer Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000011900 installation process Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to high-toughness and high-stability PVC and a preparation method thereof, belonging to the technical field of modified plastics. The high-toughness and high-stability PVC comprises the following components in parts by weight: 100 parts of PVC, 2.75-5.25 parts of stabilizer, 15-25 parts of toughener, 1-20 parts of filler, 0.3-0.8 part of antioxidant and 1-5 parts of lubricant; the stabilizer comprises organic tin maleate and dipentaerythritol. The invention solves the problem of low-temperature toughness of the PVC material by limiting the contents of the stabilizing agent and the toughening agent; meanwhile, organic tin maleate and dipentaerythritol are selected as stabilizers, and through compounding of the organic tin maleate and the dipentaerythritol, the thermal stability and the low-temperature toughness of the PVC material are synergistically improved, so that the application range of the PVC material is wider.
Description
Technical Field
The invention belongs to the technical field of modified plastics, and particularly relates to high-toughness and high-stability PVC and a preparation method thereof.
Background
The polyvinyl chloride (PVC) material has the advantages of flame retardance, acid and alkali resistance, diversified processing modes and the like, is wide in modification range, can be optimized in performance in many aspects according to actual requirements, and can be widely applied to the fields of household appliances, electronics, security, automobiles and the like. The pure PVC resin has poor stability and low decomposition temperature, and can be used only by improving the thermal stability thereof through modification, and particularly, the thermal stability of the material needs to be guaranteed in an environment needing to be in contact with high temperature. The main reason for poor thermal stability of PVC is that the resin contains a large amount of unstable structures, such as allyl chloride, free chloride ions, unsaturated bonds, etc., and is easily destroyed and decomposed to generate hydrogen chloride, and the presence of hydrogen chloride further accelerates the decomposition of polyvinyl chloride, thereby causing material failure. Meanwhile, the PVC material has the characteristics of brittleness and low strength, and is easy to generate problems such as deformation damage, embrittlement and the like in the transportation and installation processes. The hard PVC plastic has poor toughness at normal temperature, low impact strength and poorer toughness at low temperature, is quickly hardened and becomes brittle when the temperature is reduced, and is very easy to crack when being impacted, so that the application of the PVC material in a low-temperature environment is limited.
The CN114685911A previously applied by the inventor of the invention discloses a thermal stability PVC, which obviously improves the thermal stability and the fluidity of the PVC through the synergistic effect of a composite heat stabilizer consisting of mercaptan organotin and maleic organotin and other components, has excellent thermal stability and good fluidity, has the melt flow rate of more than 57g/10min, can meet the requirements of thermal stability and fluidity on PVC materials in the fields of automobile manufacture and electronic and electrical appliances, can be widely applied to automobile manufacture and electronic and electric appliances, and can be widely applied to the fields of automobile manufactureIn the field of devices. However, the invention can not solve the problem of poor low-temperature toughness of PVC, and the low-temperature impact strength of the PVC with thermal stability prepared by the invention is only 5-8 KJ/m 2 。
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides PVC with high toughness and high stability and a preparation method thereof, solves the problem that PVC materials in the prior art are difficult to have high thermal stability and low temperature toughness at the same time, and enables the application of the PVC materials to be wider.
In order to achieve the purpose, the invention adopts the technical scheme that: high-toughness and high-stability PVC comprises the following components in parts by weight: 100 parts of PVC, 2.75-5.25 parts of stabilizer, 15-25 parts of toughener, 1-20 parts of filler, 0.3-0.8 part of antioxidant and 1-5 parts of lubricant; the stabilizers include organotin maleates and dipentaerythritol.
PVC is a polar non-crystalline high polymer, has poor thermal stability, is difficult to process, cannot be directly used and can be used only by modification. Due to different types and contents of the added related auxiliary agents and fillers, the properties and requirements of the prepared PVC material are different. In the prior art, the thermal stability and toughness of PVC materials are researched, but PVC materials with thermal stability and low-temperature toughness are only reported. The invention provides the PVC material which is stable in use under a high-temperature environment and high in toughness in use under a low-temperature environment by optimizing the contents of the stabilizer and the toughening agent and optimizing the type of the stabilizer, and the application range of the PVC material is enlarged. Through a large amount of experimental researches, the inventor of the application discovers that organotin maleate reacts with unstable chlorine atoms in PVC to limit initiation of HCL removal and prevent formation of a large conjugated structure, and simultaneously, addition of tin maleate on conjugated double bonds easily generates diene addition reaction with conjugated double bonds in PVC molecules to fix the conjugated double bonds and inhibit growth of the conjugated chains; and high-content hydroxyl in the dipentaerythritol can react with HCL to achieve a high-efficiency acid absorption effect. The initial and long-term stability of PVC can be improved by compounding organic tin maleate and dipentaerythritol, so that the linear structure of the PVC is always kept in a stable state and is better compatible with the toughening agent, and the low-temperature toughness of the material is improved.
As a preferred embodiment of the high-toughness and high-stability PVC of the present invention, the weight ratio of the organotin maleate to the dipentaerythritol in the stabilizer is dipentaerythritol: organotin maleates =1:2 to 16. Research shows that when the weight ratio of the organic tin maleate to the dipentaerythritol in the stabilizer is selected to be within the range, the thermal stability and the low-temperature toughness of the prepared PVC material are both improved. Preferably, the stabilizer includes 2.5 to 4 parts of organotin maleate and 0.25 to 1.25 parts of dipentaerythritol.
As a preferred embodiment of the high-toughness and high-stability PVC, the weight ratio of the organic tin maleate to the dipentaerythritol in the stabilizer is dipentaerythritol: organotin maleates =1:3 to 10. Research shows that when the weight ratio of the organic tin maleate to the dipentaerythritol in the stabilizer is selected in the range, the prepared PVC material has higher high-temperature stability and low-temperature impact resistance.
As a preferred embodiment of the high-toughness, high-stability PVC according to the invention, the PVC has a K value of from 49 to 63. The inventor of the application finds that the K value of the PVC reflects the viscosity number of the resin, and the K value directly influences the plasticizing capacity of the material and is closely related to the toughness and stability of the material.
As a preferred embodiment of the high-toughness and high-stability PVC of the present invention, the toughening agent is at least one of MBS, chlorinated polyethylene, and acrylate.
In a preferred embodiment of the high-toughness and high-stability PVC of the present invention, the filler is at least one of calcium carbonate and talc.
As a preferable embodiment of the PVC with high toughness and high stability, the antioxidant is at least one of hindered phenol antioxidants and phosphite antioxidants.
As a preferred embodiment of the high-toughness and high-stability PVC of the present invention, the lubricant is at least one of polyethylene wax, EBS, and fatty acid ester.
The invention also provides a preparation method of the PVC with high toughness and high stability, which comprises the following steps:
(1) Weighing PVC resin, a heat stabilizer, a toughening agent, a lubricant and an antioxidant, and mixing at a low speed to obtain a mixed material A;
(2) Mixing the filler with the mixed material A at a high speed, heating to 80 ℃, and placing into a cooling cylinder to obtain a mixed material B;
(3) And extruding and granulating the mixed material B by adopting a double-stage extruder to obtain the PVC with high toughness and high stability.
Preferably, the mixing speed in the step (1) is 20-40r/s; the mixing speed in the step (2) is 50-80r/s.
The invention also provides the application of the PVC with high toughness and high stability in the fields of electronic manufacturing and automobile manufacturing.
Compared with the prior art, the invention has the following beneficial effects: the invention provides PVC with high toughness and high stability, and the invention solves the problem of low-temperature toughness of PVC materials by limiting the contents of a stabilizer and a toughening agent; meanwhile, organic tin maleate and dipentaerythritol are selected as stabilizers, and through compounding of the organic tin maleate and the dipentaerythritol, the thermal stability and the low-temperature toughness of the PVC material are synergistically improved, so that the application range of the PVC material is wider.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
The raw materials used in the examples and comparative examples of the present invention are described below, but are not limited to these materials:
PVC resin A: PVC S-58, taibo industries, ltd., K value of 55-59;
PVC resin B: PVC S-400, KANEKA CORPORATION, K value of 49-53;
PVC resin C: PVC TL-800, lejin chemical Co., ltd., K value of 60-63;
PVC resin D: PVC TK-1000, shin-Etsu chemical industry society, K value is 66-68;
PVC resin E: PVC S-70, taibo industries, ltd., K value of 71-74;
thermal stabilizer a: organotin maleate, a co-product of Asahi Co., ltd., dong Hua, quzhou;
and (3) heat stabilizer B: dipentaerythritol, shandong jin Shengtai chemical Co., ltd;
and (3) a heat stabilizer C: organotin thiols, a chemical llc of Benxing Hubei;
thermal stabilizer D: zinc stearate heat stabilizer, RUP-110C, addie investments, inc.;
heat stabilizer E: epoxidized soybean oil, HM-01R, hayma group;
a toughening agent: chlorinated polyethylene, WEIPREN2135, samson chemical ltd;
filling agent: calcium carbonate, LX-103, lixin plastics, inc.;
antioxidant: hindered phenol antioxidants, RIANOX 1076, linaloon new materials ltd;
lubricant: polyethylene wax, licowax PE 520powder, clariant Corporation.
In the examples and comparative examples, the experimental methods used were conventional methods unless otherwise specified, and the materials, reagents and the like used were commercially available; and the components used in the examples and comparative examples are identical unless otherwise specified.
Examples 1 to 10 and comparative examples 1 to 10
The composition of the PVC material of examples 1-10 of the present invention is shown in table 1 below.
The composition components of the PVC materials of comparative examples 1 to 10 according to the present invention are shown in table 2 below.
The preparation method of the PVC material of the embodiment 1-10 and the comparative example 1-10 comprises the following steps: weighing the components of the PVC resin, the stabilizer, the toughening agent, the lubricant and the antioxidant according to the proportion, placing the components in a high-speed mixer for low-speed mixing, adding the filler for high-speed mixing, and discharging the materials into a cold cylinder when the material temperature reaches 80 ℃ to obtain a mixture; and extruding and granulating the mixture by adopting a double-stage extruder to obtain the PVC material.
The thermal stability and low temperature toughness of the PVC materials prepared in examples 1 to 10 and comparative examples 1 to 10 were respectively tested, and the test results are shown in table 3.
The performance test method comprises the following steps:
(1) The thermal stability test method comprises the following steps: the initial decomposition temperature of the PVC material is used as an evaluation index, and the testing instrument is a NETZSCH thermogravimetric analyzer with the model of TG 209F1. The specific test method comprises the following steps: under the nitrogen atmosphere, the temperature is raised from the normal temperature to 750 ℃ at the temperature raising speed of 20 ℃/min, and the temperature when the PVC material is decomposed by 1% by mass is the initial decomposition temperature.
(2) The low-temperature toughness test method comprises the following steps: the notched impact strength of the cantilever beam is used as an evaluation index, the test standard is GB/T1843-2008, the sample is a 4mm injection molding notched sample bar, and the sample needs to be treated in a low-temperature freezer at the temperature of-20 ℃ for 4 hours before the test.
TABLE 1 composition of PVC materials of examples 1 to 10
TABLE 2 composition of PVC materials of comparative examples 1 to 10
TABLE 3 Performance test
As can be seen from Table 3, the selection of the type of the stabilizer has a great influence on the thermal stability and low-temperature toughness of the prepared PVC material, and as can be seen from comparative examples 4 and 1 and 2, the organotin maleate and dipentaerythritol serving as the thermal stabilizer are matched with each other, so that the PVC material can be remarkably improvedThe initial decomposition temperature and low-temperature impact strength of the material; comparing examples 1 to 8 and comparative examples 7 and 8, it can be seen that when the weight ratio of organotin maleates to dipentaerythritol in the stabilizer is dipentaerythritol: organotin maleates =1: 2-16, the prepared PVC material has good thermal stability and low-temperature toughness, the initial decomposition temperature of the PVC material reaches over 240 ℃, and when the weight ratio of the organic tin maleate to the dipentaerythritol in the stabilizer is dipentaerythritol: organotin maleates =1: 3-10 hours, the prepared PVC material has better thermal stability and low-temperature toughness; comparing examples 3, 9 and 10 and comparative examples 9 and 10, it can be seen that when the K value of PVC is 49-63, the prepared PVC material has thermal stability and low-temperature toughness of more than or equal to 13.5KJ/m 2 。
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The PVC with high toughness and high stability is characterized by comprising the following components in parts by weight: 100 parts of PVC, 2.75-5.25 parts of stabilizer, 15-25 parts of toughener, 1-20 parts of filler, 0.3-0.8 part of antioxidant and 1-5 parts of lubricant; the stabilizer comprises organic tin maleate and dipentaerythritol.
2. The high toughness, high stability PVC of claim 1 wherein the weight ratio of organotin maleates to dipentaerythritol in the stabilizer is dipentaerythritol: organotin maleates =1:2 to 16.
3. High tenacity, high stability PVC according to claim 2, characterized in that the weight ratio of organotin maleates to dipentaerythritol in the stabilizer is dipentaerythritol: organotin maleates =1:3 to 10.
4. High-toughness, high-stability PVC according to claim 1, wherein the K-value of the PVC is in the range from 49 to 63.
5. The high toughness, high stability PVC of claim 1, wherein the toughening agent is at least one of MBS, chlorinated polyethylene, acrylate.
6. The high toughness, high stability PVC of claim 1 wherein the filler is at least one of calcium carbonate, talc.
7. The high-toughness and high-stability PVC according to claim 1, wherein the antioxidant is at least one of hindered phenol antioxidants and phosphite antioxidants.
8. High-toughness, high-stability PVC according to claim 1, characterized in that said lubricant is at least one of polyethylene wax, EBS, fatty acid esters.
9. Process for the preparation of high toughness, high stability PVC according to any one of claims 1 to 8, characterized in that it comprises the following steps:
(1) Weighing PVC resin, a heat stabilizer, a toughening agent, a lubricant and an antioxidant, and mixing at a low speed to obtain a mixed material A;
(2) Mixing the filler with the mixed material A at a high speed, heating to 80 ℃, and placing into a cooling cylinder to obtain a mixed material B;
(3) And extruding and granulating the mixed material B by using a double-stage extruder to obtain the PVC with high toughness and high stability.
10. Use of a high toughness, high stability PVC according to any one of claims 1 to 8 in household appliance control devices, smoke alarm devices, safety indicator lights, wire busbars.
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2022
- 2022-12-22 CN CN202211655335.8A patent/CN115948007A/en active Pending
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