CN113444367A - Heat-aging-resistant PPS composition and preparation method and application thereof - Google Patents
Heat-aging-resistant PPS composition and preparation method and application thereof Download PDFInfo
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- CN113444367A CN113444367A CN202110663319.2A CN202110663319A CN113444367A CN 113444367 A CN113444367 A CN 113444367A CN 202110663319 A CN202110663319 A CN 202110663319A CN 113444367 A CN113444367 A CN 113444367A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/02—Polythioethers; Polythioether-ethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The invention discloses a heat-aging-resistant PPS composition and a preparation method and application thereof, wherein the composition comprises a main resin and an additive, wherein the main resin is PPS resin, and the dosage of the main resin is 30-98 parts; the additive comprises: 10-70 parts of a reinforcing material; 0.1-8 parts of epoxy resin; 0.1-2 parts of an antioxidant; 0-10 parts of a processing aid; the epoxy equivalent of the epoxy resin is 0.04-0.4 (100 g/g). The addition of the epoxy resin can increase the density of the amorphous region of the PPS resin, reduce the oxygen transmission rate, and effectively prevent the interior of a sample strip from being further degraded due to oxidation through the synergistic effect of the epoxy resin and the antioxidant, so that the thickness of the carbon layer is lower, the 1800h performance retention rate reaches over 50 percent, and the tensile property is more than or equal to 160 MPa.
Description
Technical Field
The invention relates to the technical field of special engineering plastics, and particularly relates to a heat aging resistant PPS composition and a preparation method and application thereof.
Background
Polyphenylene Sulfide (PPS) has excellent heat resistance, solvent resistance, high dimensional stability, dielectric property, flame retardance and mechanical property, and is widely applied to the fields of electronics, electrics, automobiles, machinery, chemical engineering and the like. Because the molecular chain of the PPS is formed by alternately connecting a benzene ring and a sulfur atom, only two electrons participate in bonding on the S atom, and two pairs of lone-pair electrons remain, the PPS material is easily oxidized by oxygen in the processing and using processes, and particularly under the condition of high temperature, the performance of the PPS material is reduced, and the color is darkened.
At present, in order to improve the thermal aging resistance, an antioxidant is generally added into resin, for example, Chinese patent (CN110540710A) discloses a thermal aging resistance polypropylene nano composite material and a preparation method thereof, wherein the antioxidant is added into the composite material; the heat aging resistance mode still relies on a passive oxidation resistance mode of decomposing peroxide by an antioxidant and scavenging free radicals to improve the heat aging resistance effect, and the heat aging resistance effect is limited.
Disclosure of Invention
The invention provides a heat aging resistant PPS composition for overcoming the defect of insufficient heat aging resistant performance.
Another object of the present invention is to provide a method for preparing the heat aging resistant PPS composition.
Another object of the present invention is to provide the use of said heat aging resistant PPS composition.
In order to achieve the purpose, the invention adopts the technical scheme that:
the heat aging resistant PPS composition comprises a main body resin and an additive, wherein the main body resin is a PPS resin, and the dosage of the main body resin is 30-98 parts; the additive comprises: 10-70 parts of a reinforcing material; 0.1-8 parts of epoxy resin; 0.1-2 parts of an antioxidant; 0-10 parts of a processing aid;
the epoxy equivalent of the epoxy resin is 0.04-0.4 (100 g/g).
Generally, epoxy resin is used as a compatilizer in a polyphenylene sulfide composition to improve the compatibility of two incompatible resins, or to improve the compatibility of the resin and a toughening agent, so as to ensure that the mechanical properties of the resin are not reduced; the inventor surprisingly finds that the thermal aging resistance of the material can be greatly improved by adding the epoxy resin into the PPS resin, because the density of an amorphous region in the PPS resin can be increased and the oxygen transmission rate can be reduced by adding the epoxy resin, and the further degradation caused by oxidation of the interior of a sample strip can be effectively prevented by the synergistic effect of the epoxy resin and an antioxidant. When the epoxy equivalent of the epoxy resin is less than 0.04(100g/g), the thermal aging resistance is not remarkably improved, and when the epoxy equivalent exceeds 0.4(100g/g), the fluidity is lowered, the processing is difficult and the tensile properties are also affected.
Preferably, the epoxy resin has an epoxy equivalent of 0.1 to 0.2(100 g/g).
The epoxy resin has good thermal aging resistance and processability when the epoxy equivalent is 0.1-0.2 (100 g/g).
The epoxy equivalent is determined by acid-base titration.
Preferably, the epoxy resin is a bisphenol a type epoxy resin.
The bisphenol A epoxy resin further prevents oxygen from entering due to poor air permeability, and improves the heat aging resistance.
Preferably, the reinforcing material is one or both of glass fibers or carbon fibers.
Preferably, the weight average molecular weight of the PPS resin is 5000-20000.
Preferably, the antioxidant is one or more of hindered phenol antioxidants, hindered amine antioxidants, phosphite antioxidants, thioester antioxidants and inorganic salt antioxidants.
Preferably, the processing aid is a lubricant.
And 0-2 parts of a lubricant.
The lubricant is one or more of pentaerythritol ester lubricant, silicone lubricant, stearic acid lubricant, stearamide lubricant or paraffin lubricant;
the preparation method of the heat aging resistant PPS composition comprises the following steps:
s1, respectively weighing PPS resin, epoxy resin, a processing aid and an antioxidant, and blending the raw materials uniformly to obtain a premix;
s2, feeding the reinforcing material from a side feeding port, adding the premix obtained in the step S1 into an extruder, and carrying out melting, extrusion and granulation to obtain the PPS composition.
Preferably, the processing temperature of the extruder is 190-285 ℃.
The thermal aging resistant PPS composition is applied to the preparation of transportation, household appliances, building materials, electronic appliances or aerospace products.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a heat-aging-resistant PPS composition, wherein the addition of epoxy resin can increase the density of an amorphous region of PPS resin and reduce the oxygen transmission rate, and the epoxy resin can effectively prevent the internal part of a sample bar from being further degraded due to oxidation through the synergistic effect with an antioxidant, so that the thickness of a carbon layer is lower, the 1800h performance retention rate reaches over 50 percent, and the tensile property is more than or equal to 160 MPa.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, but the embodiments of the present invention are not limited thereto.
The reagents, methods and equipment adopted by the invention are conventional in the technical field if no special description is given.
The following examples and comparative examples employ the following starting materials:
PPS resin A: weight average molecular weight of 5000, PPS 11200C, New blend
PPS resin B: weight average molecular weight 10000, PPS 11100C, New blend
PPS resin C: weight average molecular weight 20000, PPS 1150C, New blend
PPS resin D: weight average molecular weight 30000, PPS 1130C, New blend
The reinforcing material A: glass fibers; boulder group, E7CS 10-03-584H;
and (3) a reinforcing material B: carbon fibers; PX35CA0250-65, Tolli corporation;
epoxy resin a 1: bisphenol a type epoxy resin; e-20, epoxy equivalent of 0.2(100g/g), Wuxi Lanxing petrochemical company, Limited liability company;
epoxy resin B: bisphenol F type epoxy resins; YDF-161, epoxy equivalent 0.4(100 g/g); chemical engineering of national city;
epoxy resin C: bisphenol S type epoxy resin; CW-1100, epoxy equivalent 0.4(100 g/g); ciba Bioengineering, Inc. of Podocidae, Cib;
epoxy resin a 2: bisphenol a type epoxy resin; e-06, epoxy equivalent of 0.04(100g/g), Wuxi Lanxing petrochemical company, Ltd;
epoxy resin a 3: bisphenol a type epoxy resin; e-10, epoxy equivalent of 0.08(100g/g), Wuxi Lanxing petrochemical company, Inc.;
epoxy resin a 4: bisphenol a type epoxy resin; e-14, epoxy equivalent of 0.1(100g/g), Wuxi Lanxing petrochemical company, Inc.;
epoxy resin a 5: bisphenol a type epoxy resin; e-20, epoxy equivalent of 0.18(100g/g), Wuxi Lanxing petrochemical company, Inc.;
epoxy resin a 6: bisphenol a type epoxy resin; e-44, epoxy equivalent of 0.4(100g/g), Wuxi Lanxing petrochemical company, Inc.;
epoxy resin a 7: bisphenol a type epoxy resin; e-51, epoxy equivalent of 0.51(100g/g), Wuxi Lanxing petrochemical company, Inc.;
antioxidant: hindered phenolic antioxidants, 1098, commercially available;
processing aid: lubricant LOXIOL G32, a popular plasticizer in Guangzhou
The present invention will be described in detail with reference to examples and comparative examples.
The PPS compositions in the embodiments and the comparative examples of the invention are prepared by the following method, and the components are weighed according to the weight ratio shown in tables 1-3, and the specific steps are as follows:
s1, respectively weighing PPS resin, epoxy resin, a processing aid and an antioxidant, and blending the raw materials uniformly to obtain a premix;
s2, feeding the reinforcing material from a side feeding port, adding the premix obtained in the step S1 into an extruder, and carrying out melting, extrusion and granulation to obtain the PPS composition.
Examples 1 to 4
This example provides a series of heat aging resistant PPS compositions, the specific formulations of which are shown in Table 1.
TABLE 1 formulations of examples 1-4
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| PPS resin B | 60 | 60 | 60 | 60 | 60 |
| Epoxy resin A1 | 3 | — | — | 3 | 3 |
| Epoxy resin B | — | 3 | — | — | — |
| Epoxy resin C | — | — | 3 | — | — |
| Reinforcing Material A | 40 | 40 | 40 | — | 40 |
| Reinforcing material B | — | — | — | 40 | — |
| Antioxidant agent | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Processing aid | — | — | — | — | 0.2 |
Examples 6 to 12
This example provides a series of heat aging resistant PPS compositions, the specific formulations of which are shown in Table 2.
TABLE 2 formulations of examples 6-12
Examples 13 to 15 and comparative examples 1 to 3
The present examples and comparative examples provide a series of heat aging resistant PPS compositions, the specific formulations of which are set forth in Table 3.
TABLE 3 formulations of examples 13-15 and comparative examples 1-3
The above examples and comparative examples provide a series of heat aging resistant PPS compositions that were subjected to the following performance tests:
and (3) testing thermal aging resistance: and (4) carrying out aging test on the sample strips according to the UL746B-2018 standard, wherein the temperature of an aging box is 250 ℃, and the aging time is 1800 hours.
Thickness of the carbon layer: the thickness of the carbon layer of the cross section is measured by a Leica optical measurement microscope, a test sample strip is injected according to the ISO 5271 BA standard, the width of the sample strip is 5mm, and the thickness is 3 mm.
TABLE 4 Performance test data for examples and comparative examples
From examples 1 to 4, the bisphenol A type epoxy resin is significantly superior to bisphenol S type and bisphenol F type epoxy resins in the effect of improving the heat aging resistance.
From the examples 1 and 5-9, the higher the epoxy content, the better the reactivity with PPS resin, the higher the finished product compactness, the better the heat aging resistance effect; however, too high epoxy value causes rapid deterioration of fluidity, deterioration of processability and deterioration of strength, so that the epoxy value is preferably 0.1 to 0.2(100 g/g).
From examples 1 and 10 to 12, the lower the molecular weight of the PPS resin, the higher the amorphous content, and the lower the performance retention rate; the higher the molecular weight, the higher the crystalline domain content and the lower the air permeability, the higher the performance retention, but too high a molecular weight leads to a decrease in the terminal group content and a decrease in the reactivity with the epoxy resin, and a decrease in the performance retention. Therefore, the molecular weight is preferably 5000 to 20000.
From comparative examples 1-3, in comparative example 1, no epoxy resin is added, only an antioxidant is used, the heat-resistant aging performance is not good, the carbon layer is high in thickness, and the heat-resistant aging performance is not improved enough; in comparative example 2, no antioxidant is added, and the antioxidant cannot form a synergistic effect with epoxy resin, so that the anti-aging effect is not obvious, and in comparative example 3, the epoxy value is too high, so that the fluidity is greatly reduced, even stress points are formed, so that the initial strength is reduced, the processing performance is reduced, and the tensile property is greatly reduced.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. The heat aging resistant PPS composition is characterized by comprising a main body resin and an additive, wherein the main body resin is a PPS resin, and the main body resin is used in an amount of 30-98 parts; the additive comprises: 10-70 parts of a reinforcing material; 0.1-8 parts of epoxy resin; 0.1-2 parts of an antioxidant; 0-10 parts of a processing aid;
the epoxy equivalent of the epoxy resin is 0.04-0.4 (100 g/g).
2. The heat aging resistant PPS composition as defined in claim 1, wherein said epoxy resin has an epoxy equivalent of 0.1 to 0.2(100 g/g).
3. The heat aging resistant PPS composition as defined in claim 1, wherein said epoxy resin is a bisphenol A type epoxy resin.
4. The heat aging resistant PPS composition as defined in claim 1 wherein the reinforcing material is one or both of glass fibers or carbon fibers.
5. The heat aging resistant PPS composition as defined in claim 1, wherein said PPS resin has a weight average molecular weight of 5000 to 20000.
6. The heat aging resistant PPS composition according to claim 1, wherein the antioxidant is one or more of hindered phenol type antioxidant, hindered amine type antioxidant, phosphite type antioxidant, thioester type antioxidant or inorganic salt type antioxidant.
7. The heat aging resistant PPS composition as defined in claim 1, wherein said processing aid is a lubricant.
8. The method for preparing a heat aging resistant PPS composition according to any of claims 1 to 7, comprising the steps of:
s1, respectively weighing PPS resin, epoxy resin, a processing aid and an antioxidant, and blending the raw materials uniformly to obtain a premix;
s2, feeding the reinforcing material from a side feeding port, adding the premix obtained in the step S1 into an extruder, and carrying out melting, extrusion and granulation to obtain the PPS composition.
9. The method for preparing the heat aging resistant PPS composition according to claim 8, wherein the processing temperature of the extruder is 190-285 ℃.
10. Use of the heat aging resistant PPS composition of any one of claims 1 to 7 in the preparation of transportation, household appliances, building materials, electronic appliances or aerospace products.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651814A (en) * | 2018-11-28 | 2019-04-19 | 中广核俊尔新材料有限公司 | A kind of high activeness and quietness type polyphenyl thioether composite material and preparation method thereof |
| CN110776742A (en) * | 2019-10-09 | 2020-02-11 | 中广核俊尔(浙江)新材料有限公司 | Polyphenylene sulfide composite material for high-filling low-warpage battery module end plate and preparation method thereof |
| CN112280302A (en) * | 2020-11-13 | 2021-01-29 | 苏州纳磐新材料科技有限公司 | Warp-resistant high-strength high-toughness PPS composite material and preparation method thereof |
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- 2021-06-15 CN CN202110663319.2A patent/CN113444367A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651814A (en) * | 2018-11-28 | 2019-04-19 | 中广核俊尔新材料有限公司 | A kind of high activeness and quietness type polyphenyl thioether composite material and preparation method thereof |
| CN110776742A (en) * | 2019-10-09 | 2020-02-11 | 中广核俊尔(浙江)新材料有限公司 | Polyphenylene sulfide composite material for high-filling low-warpage battery module end plate and preparation method thereof |
| CN112280302A (en) * | 2020-11-13 | 2021-01-29 | 苏州纳磐新材料科技有限公司 | Warp-resistant high-strength high-toughness PPS composite material and preparation method thereof |
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Application publication date: 20210928 |