CN1045095C - Plasticized ethylene propylene ternary rubber zinc sulfonate product - Google Patents
Plasticized ethylene propylene ternary rubber zinc sulfonate product Download PDFInfo
- Publication number
- CN1045095C CN1045095C CN92108111A CN92108111A CN1045095C CN 1045095 C CN1045095 C CN 1045095C CN 92108111 A CN92108111 A CN 92108111A CN 92108111 A CN92108111 A CN 92108111A CN 1045095 C CN1045095 C CN 1045095C
- Authority
- CN
- China
- Prior art keywords
- zinc sulfonate
- ethylene propylene
- modified alkyd
- epdm
- alkyd resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Lubricants (AREA)
Abstract
The present invention relates to a new product of zinc sulfonate of plasticized ethylene propylene terpolymer rubber, which is characterized in that flax oil modified alkide resin or bean oil modified alkide resin is used as a plasticizing agent. The dosage of the oil modified alkide resin for plasticizing the zinc sulfonate of ethylene propylene terpolymer rubber, which is lower than 10%, is lower than that of zinc stearate conventionally used, and therefore, the glass transition temperature and the apparent melt viscosity of the ethylene propylene terpolymer rubber zinc sulfonate can be greatly reduced. The processing performance of the zinc sulfonate of ethylene propylene terpolymer rubber is improved at the processing temperature of 120DEG C more or less, and simultaneously, the mechanical property of the zinc sulfonate of ethylene propylene terpolymer rubber can also be improved.
Description
The invention belongs to the plastic shaping manufacture field.
In polymer molecular chain, introduce the ionomer that forms behind the ionic group because the physical crosslinking that the ionic association constitutes, can significantly improve polymkeric substance modulus, elongation at break, anti tear, resistance to wear, second-order transition temperature and melt viscosity etc.H·S·Makowiski etal.,Polym.Preprints,19(2),292-295(1978)。These unique character have been opened up wide prospect for it in industrial application.By with the blend of Ethylene-Propylene-Diene Monomer (EPDM) (EPDM) zinc sulfonate, can improve the polypropylene shock strength and reach 20 times, the polyethylene shock strength reaches 5 times, and can keep higher tensile strength.Therefore in polyolefine, add an amount of EPDM zinc sulfonate and be and solve polyolefin tenacity-increased and significantly do not reduce the effective way of its intensity.Xi Xu,Shaoyun Guo and Huilin Li,Polymer-Plastics Techn.& Eng.,30(7),251(1991)。Xi Xu,Xiangsheng Zeng and Huilin Li,J.Appl.Polym.Sci.,44(1992)。But the increase of melt viscosity will significantly cause the difficulty of processing; Have big difference with polyolefin melt viscosity and also to be difficult to make both blend even.The effective way that addresses this problem is to adopt softening agent.Yet generally be used for the ionomeric plasticizer consumption of plasticising big (greater than 10%), plasticizer consumption is big, and ionomeric intensity will descend.EPDM sulfonate is the ionomer that new development in nearly ten years is got up, and excellent property according to relevant report, with alcohols, phthalate, stearic acid and its esters plasticising EPDM sulfonate, its apparent melt viscosity is reduced, but intensity also descends.H·S·Makowiski andR·D·Lundberg,Adv.Chem.Ser.,37,187(1980)；H·S·Makowiski et al.,Am.Chem.Soc.,Polym.Preprint,20(2),281(1979)。Adopting Zinic stearas in recent years is softening agent, though can improve ionomeric mechanical property and improve processing characteristics, temperature will just begin melt-flow up to 160 ℃, and consumption is up to 10%.H·S·Makowiski etal.,Polymer Preprints,19(2),304(1978)；R.D.Lundberg et al.,Polymer Preprints,19(2),310(1978)；Preferential Plasticization of Iono-meric Compounds,N·H·Canter,Edison and D·J·Buckley,Sr.,U·S·Patent 3,847,854,Nov.12,1974,to Esso Research and Engineering Co.,。
The objective of the invention is provides a kind of plastifying EPDM zinc sulfonate product innovation at the deficiencies in the prior art.Softening agent can be modification of flax oil Synolac or soya-bean oil modified alkyd resin.During with oil-modified alkyd resin plasticising EPDM zinc sulfonate, consumption little (less than 10%), can reduce the second-order transition temperature and the apparent melt viscosity of EPDM zinc sulfonate significantly, improve the processing characteristics of EPDM zinc sulfonate, processing temperature is about 120 ℃, can also improve the mechanical property of EPDM zinc sulfonate simultaneously.
The recipe ingredient of ethylene propylene ternary rubber zinc sulfonate product innovation provided by the invention (by weight) is:
EPDM zinc sulfonate (sulfonation degree 1.1075mol/kg) 80-98 part
Oil-modified alkyd resin (available soya-bean oil or modification of flax oil Synolac) 2-20 part
An amount of optimum formula of solvent (cyclohexane) is formed (by weight):
97.5 parts of EPDM zinc sulfonates
2.5 parts of oil-modified alkyd resins
Solvent (cyclohexane) is an amount of
Take by weighing EPDM zinc sulfonate and oil-modified alkyd resin by above-mentioned recipe ingredient, oil-modified alkyd resin is joined in the solution of EPDM zinc sulfonate and mix, after flash distillation liquor and the drying, on twin-screw extruder, can obtain above-mentioned product innovation in mixing about 5 minutes in 120 ℃ of left and right sides.
Below provide the comparison example of EPDM zinc sulfonate and the plastifying EPDM zinc sulfonate product and the oil-modified alkyd resin plastifying EPDM zinc sulfonate product innovation of the present invention of prior art.
Comparison example 1
At room temperature an amount of acetylsulfuric acid is joined in the 5%EPDM cyclohexane solution, use the ethanol termination reaction after 30 minutes, and make EPDM zinc sulfonate solution, flashed solvent then, vacuum-drying with zinc acetate neutralization.The sulfonation degree that records the EPDM zinc sulfonate is 1.1075mol/kg, 136 ℃ of second-order transition temperatures.
Comparison example 2
EPDM zinc sulfonate 180 grams and Zinic stearas 20 grams that above-mentioned comparison example 1 makes are mixing 5 minutes in 180 ℃ of temperature on twin-screw extruder, the apparent melt viscosity of the plastifying EPDM zinc sulfonate that obtains, second-order transition temperature and mechanical property are respectively as Fig. 1, shown in table 1 and the table 2.
Soya-bean oil modified alkyd resin (containing soya-bean oil 43%) 5 grams and EPDM zinc sulfonate 195 grams that comparative example 1 makes are mixed in solution, the flashed solvent after drying, on twin-screw extruder,, can obtain zinc sulfonate product with soya-bean oil modified alkyd resin plastifying EPDM in mixing 5 minutes of 120 ℃ of temperature.Get 10 gram soya-bean oil modified alkyd resins (containing soya-bean oil 43%) and 190 gram EPDM zinc sulfonates equally, or get 20 gram soya-bean oil modified alkyd resins (containing soya-bean oil 43%) and 180 gram EPDM zinc sulfonates, make soya-bean oil modified alkyd resin plastifying EPDM zinc sulfonate product under these conditions, Fig. 1, shown in table 1 and the table 2, be respectively apparent melt viscosity, second-order transition temperature and the mechanical property of these plastifying EPDM zinc sulfonate.
Embodiment 2
EPDM zinc sulfonate 180 grams that 20 gram modification of flax oil Synolac (containing oleum lini 55%) and comparison example 1 are made mix in solution, the flashed solvent after drying, on twin-screw extruder,, can obtain zinc sulfonate product with modification of flax oil Synolac plastifying EPDM in mixing 5 minutes of 120 ℃ of temperature.Getting 20 gram modification of flax oil Synolac (containing oleum lini 60%) equally mixes in solution with the EPDM zinc sulfonate that 180 gram comparison example 1 make, the flashed solvent after drying, on twin-screw extruder,, obtain zinc sulfonate product with modification of flax oil Synolac plastifying EPDM in mixing 5 minutes of 120 ℃ of temperature.Be respectively the apparent melt viscosity and the second-order transition temperature of these plastifying EPDM zinc sulfonate that records shown in Fig. 2 and the table 1.
Fig. 1 is with the * that concerns of the apparent melt viscosity of soya-bean oil modified alkyd resin plastifying EPDM zinc sulfonate and shearing rate
* probe temperature is 190 ℃; 1-Zinic stearas 10%; 2-soya-bean oil modified alkyd resin 2.5%; 3-soya-bean oil modified alkyd resin 5%; 4-soya-bean oil modified alkyd resin 10%.
Fig. 2 is with the * that concerns of the apparent melt viscosity of modification of flax oil Synolac plastifying EPDM zinc sulfonate and shearing rate
* probe temperature is 190 ℃; A-Zinic stearas 10%; B-oleum lini (containing oleum lini 60%) modified alkyd resin 10%; C-oleum lini (containing oleum lini 55%) modified alkyd resin 10%.
Table 1 second-order transition temperature (Tg) of oil-modified alkyd resin plastifying EPDM zinc sulfonate
*
| Sample | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
| Tg(℃) | 136 | -59 | -55 | -57 | -58 | -50 | -48 |
* 1-EPDM zinc sulfonate; 2-Zinic stearas 10%; 3-oleum lini (containing oleum lini 60%) modified alkyd resin 10%; 4-oleum lini (containing oleum lini 55%) modified alkyd resin 10%; 5-soya-bean oil (containing soya-bean oil 43%) modified alkyd resin 10%; 6-soya-bean oil (containing soya-bean oil 43%) modified alkyd resin 5%; 7-soya-bean oil (containing soya-bean oil 43%) modified alkyd resin 2.5%.
Table 2 mechanical property of soya-bean oil modified alkyd resin plastifying EPDM zinc sulfonate
*
| Sample | 1 | 2 | 3 | 4 |
| Tensile strength (MPa) elongation at break (%) | 9.11 584 | 17.2 800 | 14.1 700 | 9.73 553 |
* the 1-Zinic stearas 10%; 2-soya-bean oil modified alkyd resin 2.5%; 3-soya-bean oil modified alkyd resin 5%; 4-soya-bean oil modified alkyd resin 10%.
Plastifying EPDM zinc sulfonate product of the present invention with relatively have following advantage with Zinic stearas plastifying EPDM zinc sulfonate:
1. EPDM zinc sulfonate processing temperature is reduced significantly, reduce to about 120 ℃ by 180 ℃;
2. the oil-modified alkyd resin consumption is less than 10%;
3. use the second-order transition temperature and the apparent melt viscosity of oil-modified alkyd resin plastifying EPDM zinc sulfonate to reduce significantly.
4. significantly improved the mechanical property of EPDM zinc sulfonate.
Claims (3)
1. plastifying ethylene propylene ternary rubber zinc sulfonate product, its characteristics are that the recipe ingredient (by weight) of this product is:
Ethylene propylene ternary rubber zinc sulfonate 80-98 part
Oil-modified alkyd resin 2-20 part
Hexanaphthene is an amount of
2. according to the described plastifying ethylene propylene ternary rubber zinc sulfonate product of claim 1, it is characterized in that the recipe ingredient (by weight) of this product is:
97.5 parts of ethylene propylene ternary rubber zinc sulfonates
2.5 parts of oil-modified alkyd resins
Hexanaphthene is an amount of
3. according to claim 1 or 2 described plastifying ethylene propylene ternary rubber zinc sulfonate products, wherein said oil-modified alkyd resin is soya-bean oil modified alkyd resin or modification of flax oil Synolac.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92108111A CN1045095C (en) | 1992-05-03 | 1992-05-03 | Plasticized ethylene propylene ternary rubber zinc sulfonate product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92108111A CN1045095C (en) | 1992-05-03 | 1992-05-03 | Plasticized ethylene propylene ternary rubber zinc sulfonate product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1078482A CN1078482A (en) | 1993-11-17 |
| CN1045095C true CN1045095C (en) | 1999-09-15 |
Family
ID=4943234
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92108111A Expired - Fee Related CN1045095C (en) | 1992-05-03 | 1992-05-03 | Plasticized ethylene propylene ternary rubber zinc sulfonate product |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1045095C (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0086069A2 (en) * | 1982-02-02 | 1983-08-17 | Uniroyal, Inc. | Blends of elastomers and nylon, and process for preparing blends |
| JPS59172529A (en) * | 1983-03-22 | 1984-09-29 | Ube Ind Ltd | Coating of polyamide molding |
| EP0201167A1 (en) * | 1985-03-12 | 1986-11-12 | UNIROYAL CHEMICAL COMPANY, Inc. | Asphalt elastomeric blends |
| EP0247502A1 (en) * | 1986-05-30 | 1987-12-02 | Siemens Aktiengesellschaft | Programmable logic array |
-
1992
- 1992-05-03 CN CN92108111A patent/CN1045095C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0086069A2 (en) * | 1982-02-02 | 1983-08-17 | Uniroyal, Inc. | Blends of elastomers and nylon, and process for preparing blends |
| JPS59172529A (en) * | 1983-03-22 | 1984-09-29 | Ube Ind Ltd | Coating of polyamide molding |
| EP0201167A1 (en) * | 1985-03-12 | 1986-11-12 | UNIROYAL CHEMICAL COMPANY, Inc. | Asphalt elastomeric blends |
| EP0247502A1 (en) * | 1986-05-30 | 1987-12-02 | Siemens Aktiengesellschaft | Programmable logic array |
Non-Patent Citations (1)
| Title |
|---|
| 《塑料手册》 1991.2.1 区英鸿主编，兵器工业出版社出版 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1078482A (en) | 1993-11-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE2646480C3 (en) | Process for the manufacture of olefin thermoplastic elastomers | |
| EP0335649B2 (en) | Graft copolymers and blends thereof with polyolefins | |
| DE2726177C2 (en) | ||
| CN110041624B (en) | TPV material and preparation method and application method thereof | |
| DE69815032T2 (en) | Thermoplastic vulcanizates made of condensation resin and cross-linked elastomer | |
| US20080206503A1 (en) | Solid concentrate composition for polymeric chain extension | |
| DE19622059A1 (en) | Thermoplastic elastomer compsn. with high heat distortion resistance | |
| DE69722153T2 (en) | Multi-component thermoplastic elastomer composition | |
| EP0532234A1 (en) | Poly (vinyl chloride) blends and additives therefor | |
| DE2848448A1 (en) | ELASTOPLASTIC PREPARATION MADE OF POLYOLEFIN RESIN AND PHENOLICALLY HARDENED EPDM RUBBER | |
| CN104292821A (en) | Nylon toughening masterbatch and preparation method thereof | |
| EP0211154B1 (en) | Impact-resistant cured objects made of ternary polyolefinic moulding compositions, and their preparation | |
| DE4330356A1 (en) | Modified elastomeric polypropylenes | |
| CN1045095C (en) | Plasticized ethylene propylene ternary rubber zinc sulfonate product | |
| CN111138754A (en) | High-fluidity and high-rigidity alloy composite material and preparation method thereof | |
| CN1712441A (en) | Production of thermoplastic elastomer | |
| EP0330015B1 (en) | Thermoplastic polypropylene polyamide compounds, process for their manufacture and their use | |
| JPH08225702A (en) | Thermoplastic composition based on polyvinylidene fluoride | |
| US4407998A (en) | High impact polypropylene resin | |
| CN113930013B (en) | Vulcanized enhanced scratch-resistant silicone master batch and preparation method thereof | |
| CN107540935B (en) | Polypropylene reclaimed material composition and preparation method thereof | |
| CN1388165A (en) | Prepn of high-toughness and high-flowability modified polypropylene agglomerate | |
| SK50099A3 (en) | Polyolefins having greater than 5 percent 2-hydroxyethyl methacrylate grafted thereto | |
| DE3636191A1 (en) | THERMOPLASTIC MOLDS | |
| CN113061312B (en) | Thermoplastic vulcanized rubber elastomer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |