CN101735534B - PVC plastic composite using salt of maleopimaric acid as thermal stabilizer - Google Patents
PVC plastic composite using salt of maleopimaric acid as thermal stabilizer Download PDFInfo
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- CN101735534B CN101735534B CN2010101010888A CN201010101088A CN101735534B CN 101735534 B CN101735534 B CN 101735534B CN 2010101010888 A CN2010101010888 A CN 2010101010888A CN 201010101088 A CN201010101088 A CN 201010101088A CN 101735534 B CN101735534 B CN 101735534B
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- maleopimaric acid
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Abstract
The invention relates to a PVC plastic composite using salt of maleopimaric acid as a thermal stabilizer. Maleopimaric acid (MPA) undergoes a salifying reaction with ZnO, MgO and the like to form the salt of the maleopimaric acid, wherein the molecular structural formula of the compound is as shown in the next figure. The product is used as the PVC thermal stabilizer and combined with other plastics aids to form a formula for preparing the processing aid of the PVC plastic product, and the dynamic fusion rheological property and the static thermal stability of the PVC materials both meet the use requirement, which proves that the salt of the maleopimaric acid obtained by the invention provides a good environmentally protected type thermal stabilizer for processing the PVC plastic product materials, wherein M is Zn, Mg or Ca.
Description
One, technical field
The invention belongs to plastic raw materials prescription modification field, particularly polyvinyl chloride plastic material products processing aid prescription modification field.
Two, background technology
Plastic heat stabilizer mainly is that the auxiliary agent that uses is produced in the PVC plastic working, and effect of crucial importance is arranged in the course of processing of plastics, and the plumbous heat stabilizer system of the current cadmium that generally uses is owing to the use that is under an embargo that environment is worked the mischief.Lead salt be thermo-stabilizer also will in the period of 2015-2020, be eliminated (execute and ask if the .PVC processing of building rising sun east is with thermo-stabilizer present situation and development [J]. polyvinyl chloride, 2009,37 (2): 1-5.).How to reduce and contain lead metal PVC goods in the pollution and the harm of producing, environment and related personnel being caused in the removal process, be the inexorable trend (Chen Yawei of China PVC plastics and international joint, Wei Haifeng, Peng adds equality. the thermal stability appraisal procedure [J] of polychloroethylene heat stabilizer. and additives for plastics, 2009,73 (1): 47-55.; Jiang Yiwen, Zhao Liangliang, Cao Changqing. the applied research [J] in hard PVC of novel thermo-stabilizer and various auxiliary heat stabilizer. plastics industry, 2009,2 (2): 47-50.).
Salt of maleopimaric acid is the rosiny deep processed product, rosin is one of important kind in the biological material, it is renewable resources, all departments have a wide range of applications in Chinese national economy, expect 2010,2015, the year two thousand twenty, the domestic market is respectively 410,000,550,000,770,000 tons to the rosiny annual requirement.Improving its utilization and economic worth, is the important topic of carrying out biological material research.
Salt of maleopimaric acid is produced to use in the PVC plastic working as plastic heat stabilizer and is not appeared in the newspapers.
Three, summary of the invention
In order to solve the serious problem of auxiliary agent environmental pollution that PVC goods that prior art exists use, the invention provides a kind of with the PVC plastics composite of salt of maleopimaric acid as thermo-stabilizer, use salt of maleopimaric acid to produce hard PVC as thermo-stabilizer, more environmental protection.
Technical scheme of the present invention is: with salt of maleopimaric acid as the PVC thermo-stabilizer, through forming with other plastic processing additives combination/cooperation screening, obtain with the PVC composition of salt of maleopimaric acid as thermo-stabilizer, each component is in weight part, and content sees the following form:
With the PVC composite formula table of salt of maleopimaric acid as thermo-stabilizer
| Recipe ingredient and specification | Add-on (weight part) |
| ?PVC | 100 |
| Salt of maleopimaric acid | 3.0～5.0 |
| The ACR impact modifier | 0.6～2.6 |
| Light calcium carbonate | 4.0～8.0 |
| Titanium oxide (rutile) | 3.5～6.5 |
| Chlorinatedpolyethylene CPE | 6.0～10.0 |
| Dioctyl phthalate (DOP) DOP | 1.0～6.0 |
That wherein PVC uses is five type PVC, ethanolic soln by using maleopimaric acid (MPA is as follows) and among ZnO, MgO or the CaO any one or several, in 30～70 ℃ of water-baths, be carried out to reactant salt, 0.2～2.0 hour reaction times, place to be crystallized separating out, filter, vacuum-drying obtains salt of maleopimaric acid, when with ZnO, MgO or CaO in during any several reaction, what obtain is exactly the maleopimaric acid composite salt.
The molecular structure of compounds formula of salt of maleopimaric acid is as follows:
Wherein, M=Zn, Mg, Ca,
Reaction equation is as follows:
In the formula, M=Zn, Mg, Ca,
With this product as the PVC thermo-stabilizer, through forming with other plastic processing additives combination/prescription screening, obtain the processing aid of PVC plastics, measure by thermal stability, dynamic fusion rheological property and the static heat stability of its thermo-stabilizer in the PVC material all reaches service requirements, proves that salt of maleopimaric acid that the present invention obtains provides a good environment-friendly type thermo-stabilizer for the processing of PVC plastic material.
With the PVC composition of salt of maleopimaric acid as thermo-stabilizer, preferred scheme is:
With the PVC composite formula table of salt of maleopimaric acid as thermo-stabilizer
| Recipe ingredient and specification | Add-on (weight part) |
| PVC (five types) | 100 |
| Salt of maleopimaric acid | 4.0 |
| The ACR impact modifier | 1.6 |
| Light calcium carbonate | 6.0 |
| Titanium oxide (rutile) | 4.5 |
| Chlorinatedpolyethylene CPE | 8.0 |
| Dioctyl phthalate (DOP) DOP | 3.0 |
Beneficial effect:
With the thermo-stabilizer of salt of maleopimaric acid (MPAM) as PVC processing, salt of maleopimaric acid can have good synergetic property with other auxiliary agent.Measure through thermal stability, its dynamic fusion rheological property and static heat stability in the PVC material all reaches service requirements, and plastics Mechanics Performance Testing overgauge index is the environment-friendly type thermo-stabilizer of the heavy metals such as novel lead-free in the PVC materials processing.
Four, embodiment
That use in an embodiment of the present invention all is the five type PVC that Qilu Petrochemical is produced, the polymerization degree 1000, and trade mark S1000, other five type PVC also have same effect.Impact modifier adopts impact modifier acrylic acid esters co-polymer commonly used just can.
MPA's is synthetic:
Electric mixer is being housed, add the 50g abietic acid in the 250mL four-hole bottle of thermometer and nitrogen conduit, 9.8g maleic anhydride, 1.92g p-methyl benzenesulfonic acid and 30mL Glacial acetic acid, after feeding nitrogen 15min, being heated to material melts substantially, open to stir and continue and evenly heat up, in treating after the temperature rise to 180 ℃, maintain the temperature at 180 ± 2 ℃, reaction 4h, cooling stops reaction, product is added the 100mL Glacial acetic acid, and stir, place after crystallization to be had separates out, obtain MPA white crystals crude product through suction filtration, crude product obtains the 55gMPA white, needle-shaped crystals after using the acetic acid recrystallization.Concrete synthetic method can reference: Cheng Zhi the chief editor, " natural resin process technology ", China Forest press, October in 1996 the 2nd edition, P260～264.
Embodiment 1
MPA 100g is dissolved in the ethanolic soln that 100ml concentration is 95%wt, adds 10g ZnO under oxygen free condition, be carried out to reactant salt in 70 ℃ of water-baths, in 0.2 hour reaction times, place and to be crystallizedly separate out filtration, vacuum-drying obtains the maleopimaric acid zinc salt.Use the maleopimaric acid zinc salt as the PVC thermo-stabilizer, obtain the PVC composite formula with other plastic processing additives combination/cooperation in the formula table.
With the PVC composite formula table of salt of maleopimaric acid as thermo-stabilizer
| Recipe ingredient and specification | Add-on (weight part) |
| PVC (five types) | 100 |
| Salt of maleopimaric acid | 3.0 |
| The ACR impact modifier | 0.6 |
| Light calcium carbonate | 4.0 |
| Titanium oxide (rutile) | 3.5 |
| Chlorinatedpolyethylene CPE | 6.0 |
| Dioctyl phthalate (DOP) DOP | 1.0 |
Embodiment 2
MPA 100g is dissolved in the ethanolic soln of 200ml 95%wt, adds 15g CaO and in 30 ℃ of water-baths, be carried out to reactant salt, in 2.0 hours reaction times, place and to be crystallizedly separate out filtration, vacuum-drying obtains the maleopimaric acid calcium salt.Use the maleopimaric acid calcium salt as the PVC thermo-stabilizer, obtain the processing composite assistants of PVC plastics with other plastic processing additives combination/cooperation in the formula table.
With the PVC composite formula table of salt of maleopimaric acid as thermo-stabilizer
| Recipe ingredient and specification | Add-on (weight part) |
| PVC (five types): | 100 |
| Salt of maleopimaric acid | 4.0 |
| The ACR impact modifier | 1.6 |
| Light calcium carbonate | 5.0 |
| Titanium oxide (rutile) | 4.5 |
| Chlorinatedpolyethylene CPE | 7.0 |
| Dioctyl phthalate (DOP) DOP | 2.0 |
Embodiment 3
MPA 100g is dissolved in the 50ml ethanolic soln, adds 15g MgO and in 70 ℃ of water-baths, be carried out to reactant salt, in 1.0 hours reaction times, place and to be crystallizedly separate out filtration, vacuum-drying obtains the maleopimaric acid magnesium salts.Use the maleopimaric acid magnesium salts as the PVC thermo-stabilizer, obtain the processing composite assistants of PVC plastics with other plastic processing additives combination/cooperation in the formula table.
With the PVC composite formula table of salt of maleopimaric acid as thermo-stabilizer
| Recipe ingredient and specification | Add-on (weight part) |
| PVC (five types): | 100 |
| Salt of maleopimaric acid | 4.5 |
| The ACR impact modifier | 1.2 |
| Light calcium carbonate | 6.0 |
| Titanium oxide (rutile) | 5.5 |
| Chlorinatedpolyethylene CPE | 8.0 |
| Dioctyl phthalate (DOP) DOP | 3.0 |
Embodiment 4
MPA 100g is dissolved in the 200ml ethanolic soln, adds 5g CaO, 5g MgO, 5g ZnO is carried out to reactant salt in 70 ℃ of water-baths, in 2.0 hours reaction times, place and to be crystallizedly separate out filtration, vacuum-drying obtains maleopimaric acid calcium, magnesium, zinc composite salt.Use maleopimaric acid calcium, magnesium, zinc composite salt as the PVC thermo-stabilizer, obtain the processing composite assistants of PVC plastics with other plastic processing additives combination/cooperation in the formula table.
With the PVC composite formula table of salt of maleopimaric acid as thermo-stabilizer
| Recipe ingredient and specification | Add-on (weight part) |
| PVC (five types): | 100 |
| Salt of maleopimaric acid | 3.8 |
| The ACR impact modifier | 0.9 |
| Light calcium carbonate | 7.0 |
| Titanium oxide (rutile) | 5.0 |
| Chlorinatedpolyethylene CPE | 9.0 |
| Dioctyl phthalate (DOP) DOP | 5.0 |
Embodiment 5
MPA 100g is dissolved in the 100ml ethanolic soln, and with 2g ZnO, 3g MgO, 5g CaO are carried out to reactant salt in 60 ℃ of water-baths, in 1.0 hours reaction times, place and to be crystallizedly separate out filtration, vacuum-drying obtains salt of maleopimaric acid.Use maleopimaric acid calcium, magnesium, zinc composite salt as the PVC thermo-stabilizer, obtain the processing composite assistants of PVC plastics with other plastic processing additives combination/cooperation in the formula table.
With the PVC composite formula table of salt of maleopimaric acid as thermo-stabilizer
| Recipe ingredient and specification | Add-on (weight part) |
| PVC (five types): | 100 |
| Salt of maleopimaric acid | 5.0 |
| The ACR impact modifier | 2.6 |
| Light calcium carbonate | 8.0 |
| Titanium oxide (rutile) | 6.5 |
| Chlorinatedpolyethylene CPE | 10.0 |
| Dioctyl phthalate (DOP) DOP | 6.0 |
More than test the analysis of the salt of maleopimaric acid MPAM that obtains: its zinc salt, get the maleopimaric acid zinc MPAZn of preparation, according to the analytical procedure of HG/T 3667-2000 Zinic stearas standard, obtain zinc content 15.92%wt; Its calcium salt obtains calcium contents 11.72%wt; Its magnesium salts obtains Mg content 7.55%wt;
Use above prescription through ordinary method, as use high mixer to mix, carry out heat stability testing with congo red method at 180 ℃ then, or high mixer mixing back is pressed on two roller machine temperature required mixing, make the required flaky material of test behind the mixing 9min, the result is as follows:
1. static stability test result (congo red method, 180 ℃) sees the following form:
| Heat-stable time (min) | 0 | 10 | 20 | 30 | 40 | 50 | 60 | 65.25 |
| Colour-change | Colourless | Pale yellow | Yellow | Reddish brown | Reddish brown | Reddish brown | Reddish brown | Black |
Static stability time 65.25min.
2, take by weighing each component by the material quantity in the formula table, mix, get 60g and on rheometer, test, initial value rotating speed: 30.0rpm with high mixer; Expect warm test point: 190.4 ℃; Milling device test point: T
1=179.9 ℃, T
2=180.7 ℃, T
3=179.6 ℃. The result of dynamic test such as following table:
| Project | Interval | Time (t)/s | The commentaries on classics distance/(Nm) | The material temperature/℃ |
| Load the peak | A | 58 | 47.3 | 169.3 |
| Minimum value | B | 73 | 28.5 | 165.2 |
| Merge the peak | X | 78 | 30.0 | 169.0 |
| Maximum value | C | 90 | 29.9 | 175.6 |
| Equilibrium state | E | 645 | 20.1 | 201.8 |
Time of fusion t
X-t
A=20s
3, plastics Mechanics Performance Testing such as following table:
| Classification | Tensile strength (MPa) | Standard index (MPa) | Reference standard number | The sample preparation condition |
| Hard product | 42.3 | ≥36.8 | GB?8814-88 | 190 ℃, mixing 9min |
Draw from above measurement result, salt of maleopimaric acid PVC thermo-stabilizer can have good synergetic property with other auxiliary agent, uses MPA and ZnO, MgO, CaO to be carried out to reactant salt and obtains salt of maleopimaric acid MPAM.This product is used for thermo-stabilizer, measure through thermal stability, its dynamic fusion rheological property and static heat stability in the PVC material all reaches service requirements, and plastics Mechanics Performance Testing overgauge index is the unleaded environment-friendly type thermo-stabilizer that waits heavy metal of PVC materials processing.
Claims (3)
1. one kind with the PVC plastics composite of salt of maleopimaric acid as thermo-stabilizer, it is characterized in that, in weight part, consists of:
2. as claimed in claim 1 with the PVC plastics composite of salt of maleopimaric acid as thermo-stabilizer, it is characterized in that described salt of maleopimaric acid thermo-stabilizer is by any one or a few is carried out to reactant salt and obtains among the ethanolic soln of maleopimaric acid and ZnO, MgO, the CaO.
3. as claimed in claim 2ly it is characterized in that,, consist of in weight part with the PVC plastics composite of salt of maleopimaric acid as thermo-stabilizer:
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101010888A CN101735534B (en) | 2010-01-22 | 2010-01-22 | PVC plastic composite using salt of maleopimaric acid as thermal stabilizer |
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|---|---|---|---|
| CN2010101010888A CN101735534B (en) | 2010-01-22 | 2010-01-22 | PVC plastic composite using salt of maleopimaric acid as thermal stabilizer |
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| CN101735534A CN101735534A (en) | 2010-06-16 |
| CN101735534B true CN101735534B (en) | 2011-12-14 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86102197A (en) * | 1985-04-06 | 1986-10-01 | 亨克尔两合股份公司 | The tackiness agent of hard PVC mould |
| CN85104049A (en) * | 1984-05-08 | 1986-11-26 | 钟渊化学工业株式会社 | The mixture of vinyl chloride-base polymer |
| CN85105177A (en) * | 1985-06-29 | 1986-12-24 | 卫生部上海生物制品研究所 | Polyvinyl chloride flexible microcellular Sptting plate and manufacture method thereof |
-
2010
- 2010-01-22 CN CN2010101010888A patent/CN101735534B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85104049A (en) * | 1984-05-08 | 1986-11-26 | 钟渊化学工业株式会社 | The mixture of vinyl chloride-base polymer |
| CN86102197A (en) * | 1985-04-06 | 1986-10-01 | 亨克尔两合股份公司 | The tackiness agent of hard PVC mould |
| CN85105177A (en) * | 1985-06-29 | 1986-12-24 | 卫生部上海生物制品研究所 | Polyvinyl chloride flexible microcellular Sptting plate and manufacture method thereof |
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Owner name: GUANGXI DINGHONG RESIN CO., LTD. Free format text: FORMER OWNER: FOREST PRODUCTS CHEMICAL INDUSTRY INST., CHINA FORESTRY SCIENCE RESEARCH ACADEMY Effective date: 20150522 |
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Effective date of registration: 20150522 Address after: 532203 the Guangxi Zhuang Autonomous Region Jiangzhou District of Chongzuo city Lijiang district 15 building room 602 Patentee after: Guangxi Ding Feng resin Co., Ltd. Address before: Five suojin village of Nanjing city in Jiangsu province 210042 No. 16 Patentee before: Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry |
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