CN115386191A - Compatilizer applied to PP/PS alloy - Google Patents

Compatilizer applied to PP/PS alloy Download PDF

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Publication number
CN115386191A
CN115386191A CN202211049932.6A CN202211049932A CN115386191A CN 115386191 A CN115386191 A CN 115386191A CN 202211049932 A CN202211049932 A CN 202211049932A CN 115386191 A CN115386191 A CN 115386191A
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main material
parts
weight
alloy
material component
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叶嘉鹏
董显权
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Cangzhou Nengzhiguang New Material Co ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10Homopolymers or copolymers of propene
    • C08L23/12Polypropene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/08Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers

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Abstract

The invention belongs to the technical field of high polymer materials, and particularly relates to a compatilizer applied to PP/PS (polypropylene/polystyrene) alloy, which consists of 90 to 100 parts by weight of main materials and 0 to 10 parts by weight of auxiliary materials; wherein the main material comprises at least 50 parts by weight of a first main material component and at least 20 parts by weight of a second main material component; the first main material component is styrene-butadiene-styrene copolymer, and the second main material component is an elastomer; the auxiliary materials comprise a grafting modifier, a reaction promoter, an initiator, an antioxidant, a lubricant, methyl silicone oil and linear low-density polyethylene powder. According to the invention, the styrene-butadiene block copolymer is used as a first main material, the elastomer material is used as a second main material, and the auxiliary material is matched, so that the obtained compatilizer can effectively increase the toughness and the impact resistance of the PP/PS alloy, reduce the peeling phenomenon, increase the interface bonding property of the PP/PS alloy, and has an obvious price advantage.

Description

Compatilizer applied to PP/PS alloy
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a PP/PS alloy compatilizer applied to the fields of travel cases, supports, building materials, electric appliances and the like.
Background
At present, the research and development of organic alloys are an active research field in organic polymer research, the research on organic alloys can realize the combination of favorable properties of different polymer materials, and a brand new application field is expanded, so that the requirements of industrial practice on materials are met. Compared with the research and development of polymers, the research and development cost of the organic alloy is low, the risk is low, the cost is low, the performance of the organic alloy is excellent, and the performance which is not available in both homopolymers can be developed.
The current compatilizer components commonly used in PP/PS alloy are SBS, vidamia (PP-based elastomer), POE and the like. SBS is styrene-butadiene-styrene block copolymer, is a material with large output and low cost in SBCs, is beneficial to industrial production, has the performances of plastics and rubber, and can improve the impact resistance of organic alloy. The Widamei is a common propylene-based elastomer, has good coating performance, can be well compatible with various materials, and has excellent processability. POE is a copolymer of ethylene and octene, which is a thermoplastic elastomer with excellent properties and is widely used in nylon (PA) and polypropylene (PP) polymer materials.
The PP/PS alloy is mainly formed by blending and modifying PP/PS, but the compatibility of the PP/PS alloy and the PP/PS is poor, the PP/PS alloy is difficult to disperse in the components of the other party when the PP/PS alloy is directly subjected to melt blending, and the formed blend is relatively coarse in dispersion, poor in mechanical property and easy to generate a peeling phenomenon, so that the problem of the compatibility and the interface caking property of the PP and the PS is the key for preparing the PP/PS alloy.
Disclosure of Invention
In order to overcome the defects of the prior art, the inventor finds that the styrene-butadiene block copolymer (SBS) can effectively increase the toughness and the impact resistance of the PP/PS alloy and reduce the peeling phenomenon, not only can increase the interface bonding property of the PP/PS alloy, but also can increase the toughness and the impact resistance of the alloy, and has obvious price advantage through a great deal of research.
Therefore, the invention aims to provide a compatilizer applied to PP/PS alloy, which consists of 90 to 100 weight parts of main materials and 0 to 10 weight parts of auxiliary materials; wherein the content of the first and second substances,
the main material comprises at least 50 parts by weight of a first main material component and at least 20 parts by weight of a second main material component; the first main material component is styrene-butadiene-styrene copolymer, and the second main material component is an elastomer; specifically, the content of the second main material component is less than or equal to that of the first main material component;
the auxiliary materials comprise a grafting modifier, a reaction promoter, an initiator, an antioxidant, a lubricant, methyl silicone oil and linear low-density polyethylene powder (LLDPE powder).
Further, in a preferred embodiment, the first main material component comprises 50 to 80 parts by weight of a styrene-butadiene-styrene block copolymer, and the second main material component comprises 20 to 50 parts by weight of a second main material component, wherein the second main material component is selected from one or more of ethylene-butylene elastomer (POE), widamel (propylene-based elastomer), hydrogenated styrene-butadiene block copolymer (SEBS), metallocene (mPE) or elastomer compounded copolymers.
Further, in a preferred embodiment, the graft modifier is selected from one or more of acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, maleic Anhydride (MAT), itaconic anhydride, crotonic anhydride, and citraconic anhydride.
Further, in a preferred embodiment, the co-reactant is a monoolefin monomer selected from one or both of styrene (St) and Divinylbenzene (DVB).
Further, in a preferred embodiment, the initiator is a peroxide type initiator selected from one or more of 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane (DTBH), dicumyl peroxide (DCP) and dibenzoyl peroxide (BPO).
Further, in a preferred embodiment, the antioxidant is selected from one or more of pentaerythritol tetrakis [ β - (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010), tris (2,4-di-tert-butyl) phenyl phosphite antioxidant 168), octadecyl β (3,5 di-tert-butyl-4-hydroxyphenyl) propionate, 2,6 di-tert-butyl-p-cresol.
Further, in a preferred embodiment, the lubricant is selected from one or more of pentaerythritol stearate (PETS), silicone powder, polyethylene wax.
Further, in a preferred scheme, the composition comprises the following components in parts by weight:
Figure BDA0003823393280000031
further, in a preferred scheme, the composition comprises the following components in parts by weight:
Figure BDA0003823393280000032
Figure BDA0003823393280000041
2-7 parts of low-density polyethylene powder; specifically, the coating comprises the following components in parts by weight:
Figure BDA0003823393280000042
in some preferred embodiments, the following components are included, in particular, in parts by weight:
Figure BDA0003823393280000043
further, in a preferred embodiment, the PP/PS alloy is selected from one or more of general purpose polystyrene, high impact polystyrene, polypropylene, organic alloys and polymeric materials of mixtures thereof.
In another aspect, the invention provides a preparation method of a compatilizer for PP/PS alloy, which comprises the step of blending a main material and an auxiliary material in an extruder.
Further, in a preferred embodiment, the extruder is a twin screw extruder.
Further, in a preferred embodiment, when the methyl silicone oil is added to the auxiliary material component, the methyl silicone oil is mixed with the main material until the surface of the main material is wetted, and then the methyl silicone oil is mixed with other auxiliary material components.
In another aspect, the invention also provides the PP/PS alloy material, and the PP/PS alloy material is prepared by the compatilizer.
The invention has the beneficial effects that:
1. the PP/PS alloy compatilizer is prepared by taking the styrene-butadiene block copolymer as a first main material, taking the elastomer material as a second main material and matching auxiliary materials, and has more excellent toughness and impact resistance and wider application market when being used for PP/PS alloy materials compared with PP and PS materials;
2. the PP/PS alloy compatilizer can increase the toughness and the impact resistance of products, effectively improve the problem of poor compatibility in a PP/PS system, improve the interface bonding property and meet the industrial requirements;
3. the PP/PS alloy compatilizer can be used in the fields of travel cases, supports, building materials, electric appliances and the like, and comprises but is not limited to PP/PS alloy materials.
Detailed Description
The experimental procedures in the following examples are conventional unless otherwise specified. The raw materials in the following examples are all common commercial products and can be purchased from the market unless otherwise specified; the detection methods are all conventional detection methods unless otherwise specified.
The compatilizer comprises main materials and auxiliary materials. Wherein the content of the first and second substances,
main materials: comprises a first main component which is styrene-butadiene-styrene block copolymer (SBS) and the content of the first main component can be 50, 55, 60, 65, 70, 75 and 80 parts by weight.
In the present invention, the content of SBS is preferably 50 to 80 parts by weight, more preferably 55 to 75 parts by weight, and particularly preferably 60 to 65 parts by weight.
In addition to the first main component described above, the compatibilizer according to the present invention may also comprise a second main component, which may be an elastomeric material commonly used in the existing industrial production, such as: ethylene-propylene copolymers (POE); also, the elastomer may be a dada (propylene-based elastomer), a hydrogenated styrene-butadiene block copolymer, a metallocene, or a multi-elastomer compounded copolymer.
The content of the second major component according to the present invention may be 20, 25, 30, 35, 40, 45, 50 parts by weight (in parts by weight).
In the present invention, the content of the second major component is preferably 20 to 50 parts by weight, more preferably 30 to 40 parts by weight, and particularly preferably 35 to 40 parts by weight.
According to the invention, the content of the second main material component is less than or equal to the content of the first main material component.
Auxiliary materials: comprises a grafting modifier, a reaction promoter, an initiator, a lubricant, an antioxidant, LLDPE powder and methyl silicone oil.
According to the invention, the graft modifier may be selected from acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, maleic anhydride, itaconic anhydride, crotonic anhydride and citraconic anhydride; preferably one or more of maleic anhydride, itaconic anhydride, crotonic anhydride and citraconic anhydride; maleic Anhydride (MAH) is particularly preferred.
The graft modifiers according to the invention can be used in amounts of 0, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2 parts by weight (in parts by weight). The fraction of the graft modifier is preferably 0 or 0.5 to 1.0 part by weight, more preferably 0 or 0.6 to 0.8 part by weight.
According to the invention, the co-reactant is a monoolefin monomer, preferably selected from styrene (St) and Divinylbenzene (DVB). The co-reactant according to the present invention may be used in an amount of 0, 0.1, 0.2, 0.3, 0.4, 0.5 parts by weight, preferably in an amount of 0 to 0.5 parts by weight, more preferably 0 or 0.3 to 0.4 parts by weight (in parts by weight).
According to the invention, the initiator is of the peroxide type, preferably selected from 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane (DTBH), dicumyl peroxide (DCP) and dibenzoyl peroxide (BPO). The initiators according to the invention can be used in amounts of 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10 parts by weight (in parts by weight). The initiators are preferably used in amounts of from 0 to 0.07 part by weight, more preferably from 0 to 0.05 part by weight, and particularly preferably from 0 or from 0.2 to 0.5 part by weight.
The adjuvants according to the invention may furthermore comprise LLDPE powders and silicone oils. The LLDPE powder is mainly used for preparing auxiliary materials, MAH and an initiator can be diluted, and the stability of a product prepared by mixing the MAH and the initiator with main materials and discharging the mixture is better. The silicone oil (preferably methyl silicone oil) may be mixed with the main material until the surface is wetted and then mixed with the other pellets.
According to the invention, the silicone oil may be used in an amount of 0.1 to 0.5 parts by weight, preferably 0.2 to 0.4 parts by weight, particularly preferably 0.3 parts by weight.
According to the invention, the LLDPE powder is used in amounts of 0 to 10.0 parts by weight, preferably 0 to 7.0 parts by weight, particularly preferably 0 or 3.5 to 6 parts by weight.
In the invention, the graft modifier, the reaction promoter, the initiator, the antioxidant, the lubricant and the LLDPE powder can be not added, and the four auxiliary material components of the graft modifier, the reaction promoter, the initiator and the LLDPE powder can be added simultaneously or not added simultaneously in the test scheme.
In another aspect, the invention provides a preparation method of a compatilizer applied to PP/PS alloy, which comprises the steps of blending a main material and an auxiliary material in an extruder to obtain the compatilizer; the extruder is a twin screw extruder. When the compatilizer comprises an auxiliary material component added with silicone oil, the silicone oil and the main material are mixed until the surface of the main material is wetted, and then the main material and the other auxiliary material components are mixed.
The compatibilizer according to the present invention may be used for PP/PS alloy materials, which may be polymer materials of polypropylene (PP), general Purpose Polypropylene (GPPS), high Impact Polystyrene (HIPS), organic alloys, mixtures thereof, and the like. For example, white pollution frequently occurs in waste industrial products and household garbage, a large amount of PP and PS resin materials in waste resin materials can be used as raw materials for purification and reprocessing to prepare PP/PS alloys, and the PP/PS alloys are applied to manufacturing of some lower-end household products, including cement templates for construction sites and the like. Based on the need to reduce cost and performance, some portable household appliances that require lower density and have certain mechanical properties, such as: the PP/PS alloy and the compatilizer thereof are also needed to be used in the fields of travel suitcase pull rods, selfie sticks, crutches, brackets and the like.
The present invention is described in further detail below with reference to examples:
raw materials and equipment:
all raw materials used in the examples, for example: PP, SBS, SEBS, widamei, POE, mPE, GPPS, HIPS, GPPS and Ganzhou energy photo-new material company modified material.
The equipment used in the examples is as follows:
twin screw extruder, model HK26, available from koyama machinery ltd;
an injection molding machine, model MA900 III, available from Haitian Plastic machines group, inc.;
a miniature electronic universal tester, model CMT4204, available from Meits systems, inc.
The performance tests carried out in the examples were carried out according to the following:
tensile strength and elongation at break tests were carried out in GB/T10470-1992 with sample sizes of 150X 10X 4mm and tensile rates of 50mm/min;
flexural strength and flexural modulus tests were carried out according to GB/T3356-1996, with sample dimensions of 80X 10X 4mm and a tensile rate of 2mm/min;
notched impact strength tests were carried out in accordance with GB/T1843-1996, with specimen dimensions of 80X 10X 4mm and a notch depth of 2mm.
The preparation method of the compatilizer comprises the following steps:
the components of comparative example 1 and examples 1 to 5 shown in Table 1 were mixed, and the mixture was poured into a twin-screw extruder at a main machine rotation speed of 330r/min and a feeding speed of 20Hz, to blend the main material components and the auxiliary material components. After blending, the mixture is extruded and cut into particles for subsequent use.
Table 1: the main material component and the auxiliary material component of the compatilizer are proportioned (unit: part)
Figure BDA0003823393280000091
Preparation of injection molding samples:
the formulations of the injection-molded articles of comparative examples 3 to 5 and examples 6 to 10 are shown in Table 2. And (2) drying PP, HIPS and GPPS for 2 hours in a vacuum drying oven at 80 ℃, then respectively blending 30 parts by weight, 45 parts by weight and 20 parts by weight of the compatilizer prepared in the above way, and pouring the mixture into a double-screw extruder. See table 3 for process parameter settings for the extruder.
Table 2: ratio of injection molding samples (unit: portion)
Figure BDA0003823393280000092
Figure BDA0003823393280000101
Table 3: extruder process parameters in the preparation of injection molded part samples
Figure BDA0003823393280000102
The samples obtained from the extruder were dried in a dryer at 70 ℃ for 2 hours. And finally, pouring the dried material into an injection molding machine, and molding at the temperature of 190-210 ℃ by using the injection pressure of 75MPa and the pressure maintaining pressure of 75MPa to prepare an injection molding sample. Wherein the injection molded article sample requires neither skirt nor shrinkage.
And (3) performance testing:
the injection molded article samples of comparative examples 3 to 5 and examples 6 to 10 prepared as described above were allowed to stand for more than 2 hours to avoid the influence of internal stress on the measurement. The tensile strength, elongation at break, flexural strength, flexural modulus and impact strength were then measured using a miniature electronic universal tester. Each test data is the average of three parallel test results, which are shown in table 4.
Table 4: mechanical property test results of injection molded part samples
Figure BDA0003823393280000103
The performance test results show that the compatilizer prepared by the proportion has excellent mechanical property and impact resistance and excellent overall performance when used in alloy materials. In contrast, in comparative example 3, the impact strength of the PP/PS alloy material without the addition of the compatilizer is only 8.881KJ/m 2 The tensile strength is 15.18MPa, the elongation at break is 30.22 percent, and the performance is poorer than that of the invention; in comparative examples 4 and 5, the tensile strength, elongation at break and impact strength of the SBS compound wafer or the SBS compound POE are remarkably improved after the compatilizer is added, which shows that the main material of the invention is reasonable in proportion; proper auxiliary materials are added to further play a role in improving the mechanical property and the impact resistance; in addition, the skinning phenomenon of the articles using the compatibilizers of the present invention is improved.
Finally, it should be emphasized that the above-described preferred embodiments of the present invention are merely examples of implementations, rather than limitations, and that many variations and modifications of the invention are possible to those skilled in the art, without departing from the spirit and scope of the invention.
Furthermore, the recitation of numerical ranges by endpoints of the present invention includes all numbers subsumed within that range as well as the endpoints.
Furthermore, the preferred embodiments according to the invention can be combined with the basic embodiments of the invention either individually or in any combination. All such combinations are included within the scope of the present invention.

Claims (10)

1. The compatilizer applied to PP/PS alloy is characterized by comprising, by weight, 90-100 parts of main materials and 0-10 parts of auxiliary materials; wherein the content of the first and second substances,
the main material comprises at least 50 parts by weight of a first main material component and at least 20 parts by weight of a second main material component; the first main material component is styrene-butadiene-styrene copolymer, and the second main material component is an elastomer;
the auxiliary materials comprise a grafting modifier, a reaction promoter, an initiator, an antioxidant, a lubricant, methyl silicone oil and linear low-density polyethylene powder.
2. The compatibilizer applied to the PP/PS alloy according to claim 1, wherein the first main material component comprises 50 to 80 parts by weight of styrene-butadiene-styrene block copolymer, the second main material component comprises 20 to 50 parts by weight of second main material component, and the second main material component is one or more selected from ethylene-butylene elastomer, widamet, hydrogenated styrene-butadiene block copolymer, metallocene and multiple elastomer compound copolymer.
3. The compatibilizer applied to the PP/PS alloy according to claim 1, wherein the grafting modifier is one or more selected from acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, maleic anhydride, itaconic anhydride, crotonic anhydride and citraconic anhydride.
4. The compatibilizer applied to the PP/PS alloy according to claim 1, wherein the co-reactant is a mono-olefin monomer selected from one or two of styrene and divinylbenzene; the initiator is a peroxide type initiator and is selected from one or more of 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexane, dicumyl peroxide and dibenzoyl peroxide.
5. The compatibilizer applied to PP/PS alloy according to claim 1, wherein the antioxidant is selected from one or more of pentaerythritol tetrakis [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ], phenyl tris (2,4-di-tert-butyl) phosphite, octadecyl beta (3,5 di-tert-butyl-4-hydroxyphenyl) propionate and 2,6 di-tert-butyl-p-cresol.
6. The compatibilizer applied to PP/PS alloy according to claim 1, wherein the lubricant is one or more selected from pentaerythritol stearate, silicone powder and polyethylene wax.
7. The compatilizer applied to the PP/PS alloy according to claim 1, which is characterized by comprising the following components in parts by weight:
Figure FDA0003823393270000021
8. the compatibilizer applied to the PP/PS alloy according to claim 7 is characterized by comprising the following components in parts by weight:
Figure FDA0003823393270000022
Figure FDA0003823393270000031
9. the compatibilizer applied to the PP/PS alloy according to claim 1, wherein the PP/PS alloy is one or more selected from the group consisting of general purpose polystyrene, high impact polystyrene, polypropylene, organic alloy and a mixture thereof.
10. A PP/PS alloy material, wherein the PP/PS alloy material is prepared by the compatibilizer of any one of claims 1-9.
CN202211049932.6A 2022-08-30 2022-08-30 Compatilizer applied to PP/PS alloy Pending CN115386191A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116218127A (en) * 2023-05-08 2023-06-06 广东美的制冷设备有限公司 Compatilizer and preparation method thereof, alloy material and preparation method thereof, and refrigerator liner

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