CN115010920A - Hyperbranched cross-linking agent, high-melt-strength polypropylene and preparation method thereof - Google Patents
Hyperbranched cross-linking agent, high-melt-strength polypropylene and preparation method thereof Download PDFInfo
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- CN115010920A CN115010920A CN202210642984.8A CN202210642984A CN115010920A CN 115010920 A CN115010920 A CN 115010920A CN 202210642984 A CN202210642984 A CN 202210642984A CN 115010920 A CN115010920 A CN 115010920A
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- polypropylene
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- hyperbranched
- vinyl acetate
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- -1 polypropylene Polymers 0.000 title claims abstract description 135
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 133
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 133
- 239000003431 cross linking reagent Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 44
- 239000003963 antioxidant agent Substances 0.000 claims description 30
- 230000003078 antioxidant effect Effects 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 150000004985 diamines Chemical class 0.000 claims description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 238000001125 extrusion Methods 0.000 claims description 21
- 150000007519 polyprotic acids Polymers 0.000 claims description 20
- 239000003999 initiator Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 8
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 7
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 7
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 5
- GGAUUQHSCNMCAU-ZXZARUISSA-N (2s,3r)-butane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C[C@H](C(O)=O)[C@H](C(O)=O)CC(O)=O GGAUUQHSCNMCAU-ZXZARUISSA-N 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 238000004132 cross linking Methods 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 5
- 125000003277 amino group Chemical group 0.000 abstract description 4
- 239000000155 melt Substances 0.000 description 20
- 238000002156 mixing Methods 0.000 description 20
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 9
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000001133 acceleration Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- NWOJEYNEKIVOOF-UHFFFAOYSA-N hexane-2,2-diamine Chemical group CCCCC(C)(N)N NWOJEYNEKIVOOF-UHFFFAOYSA-N 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/06—Polyamides derived from polyamines and polycarboxylic acids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a hyperbranched cross-linking agent, high melt strength polypropylene and a preparation method thereof. The hyperbranched cross-linking agent has a hyperbranched structure, and the cross-linking agent has the effect of improving the strength of a polypropylene melt. In addition, the main groups on the surface of the hyperbranched cross-linking agent are amino groups, so that the hyperbranched cross-linking agent cannot react with a polypropylene main chain, and when high-melt-strength polypropylene is prepared, the crosslinking degree of the high-melt-strength polypropylene can be controlled, the generation of gel is controlled, and the problem of material processing performance reduction caused by the generation of gel is avoided.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a hyperbranched cross-linking agent, high-melt-strength polypropylene and a preparation method thereof.
Background
High melt strength polypropylene (HMSPP) is a high performance material in polypropylene. The high melt strength polypropylene has the melting strain hardening phenomenon, so the high melt strength polypropylene has the characteristics of strong air inclusion capability, difficult hole breaking and hole merging, melt sagging resistance and the like, and can meet the application in the fields of thermoforming, blow molding, extrusion coating, foaming and the like.
How to improve the melt strength of polypropylene has been one of the major research directions in the field of polypropylene materials. In the prior art, a long-chain branching structure is mainly introduced on a polypropylene molecular chain to improve the melt strength of polypropylene, but when a crosslinking agent is adopted for grafting on the polypropylene molecular chain, the long-chain branching structure of polypropylene is difficult to control, and the crosslinking agent can graft with a plurality of points on the polypropylene chain in the grafting process, so that gel is generated, the material quality and the material performance are influenced, and the processing performance of the obtained material is reduced.
Disclosure of Invention
The invention aims to solve the technical problems of providing a hyperbranched cross-linking agent, high melt strength polypropylene and a preparation method thereof, and solving the problems that the long-chain branched structure of the high melt strength polypropylene is difficult to control and gel is generated to cause poor material performance in the prior art.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a hyperbranched cross-linking agent is prepared from diamine and polybasic acid through reaction.
Preferably, the diamine is at least one of ethylenediamine, methylpentamethylenediamine and hexamethylenediamine;
the polybasic acid is at least one of citric acid, butanetetracarboxylic acid and ethylenediamine tetraacetic acid.
Preferably, the molecular weight of the hyperbranched cross-linking agent is 1000-8000.
Further preferably, the hyperbranched cross-linking agent obtained by reacting diamine with polybasic acid has a hyperbranched structure, and the main group on the surface is amino.
Further preferably, the weight ratio of the diamine to the polyacid is 1: (1-3).
The invention also provides a preparation method of the hyperbranched cross-linking agent, which comprises the following steps:
taking diamine and polybasic acid, and reacting at 50-120 deg.C and 20-101KPa for 30-600min to obtain the final product;
optionally, the reaction is carried out under catalyst conditions, the catalyst being triethylamine.
Further preferably, the amount of the triethylamine is 0.1% of the sum of the weight of the diamine and the weight of the polyacid.
The invention also provides high melt strength polypropylene which is obtained by the synthetic reaction of polypropylene and the hyperbranched cross-linking agent.
Preferably, the polypropylene is vinyl acetate grafted polypropylene.
Further preferably, the high melt strength polypropylene is obtained by performing a synthetic reaction between the vinyl acetate grafted polypropylene and the hyperbranched cross-linking agent in a twin-screw extrusion process.
Preferably, the vinyl acetate grafted polypropylene is prepared from the following raw materials in parts by weight: 100 parts of polypropylene, 0.02-0.3 part of initiator, 0.5-3 parts of vinyl acetate and 0.2-1 part of antioxidant.
Preferably, the initiator is at least one of tert-butyl hydroperoxide, dicumyl peroxide, Benzoyl Peroxide (BPO).
Further preferably, the polypropylene is homo-or co-linear polypropylene powder and has a melt index of 0.5-5g/10 min.
The invention also provides a preparation method of the high melt strength polypropylene, which comprises the following steps: the polypropylene and the hyperbranched cross-linking agent are uniformly mixed, and the high melt strength polypropylene is obtained through the twin-screw melt extrusion reaction at the temperature of 160 ℃ and the rotational speed of the screw of 100 ℃ and the rotational speed of 400 rpm.
Further preferably, the preparation method of the high melt strength polypropylene specifically comprises the following steps: the polypropylene, the hyperbranched cross-linking agent and the antioxidant are uniformly mixed, and the high melt strength polypropylene is obtained through a twin-screw melt extrusion reaction at the temperature of 160-200 ℃ and the screw rotation speed of 100-400 rpm.
Further preferably, the weight ratio of the polypropylene, the hyperbranched cross-linking agent and the antioxidant is 100: (0.5-5): (0.2-1).
Preferably, the polypropylene is vinyl acetate grafted polypropylene, and the preparation of the vinyl acetate grafted polypropylene comprises the following steps: the polypropylene, the initiator, the vinyl acetate and the antioxidant are uniformly mixed, and the vinyl acetate grafted polypropylene is obtained through a twin-screw melt extrusion reaction at the temperature of 160-200 ℃ and the screw rotation speed of 100-400 rpm.
The scheme of the invention at least comprises the following beneficial effects:
(1) the hyperbranched cross-linking agent is obtained by reacting diamine with polybasic acid, has a hyperbranched structure, and has the effect of improving the strength of polypropylene melt. In addition, the main groups on the surface of the hyperbranched cross-linking agent are amino groups, so that the hyperbranched cross-linking agent cannot react with a polypropylene main chain, and when high-melt-strength polypropylene is prepared, the crosslinking degree of the high-melt-strength polypropylene can be controlled, the generation of gel is controlled, and the problem of material processing performance reduction caused by the generation of gel is avoided;
(2) the high melt strength polypropylene of the invention adopts a two-step method of grafting first and then crosslinking to realize long chain branching of the polypropylene, and realizes crosslinking of the polypropylene through extrusion processing, thereby improving the melt strength of the polypropylene, and simultaneously controlling the gel content without influencing the processing performance of the high melt strength polypropylene. Specifically, the reaction is carried out by adopting the reaction of the polypropylene grafted by the vinyl acetate and the hyperbranched cross-linking agent, and the amidation reaction is carried out on the amino group on the surface of the hyperbranched cross-linking agent and the carboxyl group of the polypropylene grafted by the vinyl acetate, so that the reaction activity is high, the grafting rate is high, and the effect of improving the melt strength of the polypropylene is obvious. More importantly, the main groups on the surface of the hyperbranched cross-linking agent are amino groups, only react with grafting monomer vinyl acetate, but not react with a polypropylene main chain, so that the grafting cross-linking degree of the polypropylene with high melt strength can be better controlled, a stable and controllable long-chain branched structure of the polypropylene with excellent performance is obtained, meanwhile, the cross-linking agent is prevented from being grafted with a plurality of points on a polypropylene chain, and further the generation of gel is avoided.
Detailed Description
Those not indicated in the examples of the present invention were carried out under the conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by manufacturers, but are conventional products which can be obtained commercially, and the implementation of the technical scheme and the realization of the technical effect are not influenced by the raw materials of different manufacturers and models.
Example 1
The hyperbranched cross-linking agent of the embodiment is obtained by reacting diamine with polybasic acid. Wherein the diamine is ethylenediamine; the polybasic acid is citric acid. The molecular weight of the hyperbranched cross-linking agent is 1000.
In this embodiment, the preparation method of the hyperbranched cross-linking agent is as follows: according to the weight portion, 25 portions of diamine and 75 portions of polybasic acid are taken, 0.1 portion of triethylamine is added as a catalyst, and the mixture reacts for 600min under mechanical stirring at the temperature of 50 ℃ and the pressure of 20KPa, so that the obtained compound with the hyperbranched structure is the hyperbranched cross-linking agent, and the main group on the surface is amino.
In this embodiment, the hyperbranched cross-linking agent is used to prepare high melt strength polypropylene, which is obtained by a synthetic reaction between vinyl acetate grafted polypropylene and the hyperbranched cross-linking agent in a twin-screw extrusion process.
The vinyl acetate grafted polypropylene is prepared from the following raw materials in parts by weight: 100 parts of polypropylene, 0.3 part of the initiator, 3 parts of vinyl acetate and 0.2 part of antioxidant.
Wherein the initiator is tert-butyl hydroperoxide. The polypropylene is homopolymerized or copolymerized straight-chain polypropylene powder, and the melt index is 3g/10 min. The antioxidant is formed by mixing an antioxidant 1010 and an antioxidant 168 in a mass ratio of 2: 1.
In this example, the preparation method of the high melt strength polypropylene is as follows:
(1) the method comprises the steps of taking the polypropylene, the initiator, the vinyl acetate and the antioxidant according to the selected weight parts, uniformly mixing, and carrying out melt extrusion reaction by a double screw at the temperature of 200 ℃ and the screw rotation speed of 400rpm to obtain the vinyl acetate grafted polypropylene.
(2) Taking the vinyl acetate grafted polypropylene obtained in the step (1), the hyperbranched cross-linking agent and the antioxidant, and mixing the components in a ratio of 100: 0.5: 1, and performing melt extrusion reaction by a double screw at the temperature of 200 ℃ and the screw rotating speed of 400rpm to obtain the polypropylene with high melt strength.
In the step (2), the antioxidant is formed by mixing an antioxidant 1010 and an antioxidant 168 in a mass ratio of 2: 1.
It should be noted that the polypropylene can be replaced by other homo-or co-linear polypropylene powder with a melt index in the range of 0.5-5g/10min, and the selection of the raw material of the polypropylene does not affect the achievement of the object of the present invention. Likewise, the antioxidant is not exclusive, and those skilled in the art can select other antioxidants to replace according to actual situations, and the details are not described below.
Example 2
The hyperbranched cross-linking agent of the embodiment is obtained by reacting diamine with polybasic acid. Wherein the diamine is methylpentanediamine; the polybasic acid is butanetetracarboxylic acid. The molecular weight of the hyperbranched cross-linking agent is 8000.
In this embodiment, the preparation method of the hyperbranched cross-linking agent is as follows: according to the weight portion, 40 portions of diamine and 60 portions of polybasic acid are taken, 0.1 portion of triethylamine is added as a catalyst, and the mixture reacts for 300min under mechanical stirring at the temperature of 80 ℃ and the pressure of 80KPa, so that the obtained compound with the hyperbranched structure is the hyperbranched cross-linking agent, and the main group on the surface is amino.
In this embodiment, the hyperbranched cross-linking agent is used to prepare high melt strength polypropylene, which is obtained by a synthetic reaction between vinyl acetate grafted polypropylene and the hyperbranched cross-linking agent in a twin-screw extrusion process.
The vinyl acetate grafted polypropylene is prepared from the following raw materials in parts by weight: 100 parts of polypropylene, 0.02 part of the initiator, 0.5 part of vinyl acetate and 0.6 part of antioxidant.
Wherein the initiator is dicumyl peroxide. The polypropylene is copolymerized straight-chain polypropylene powder, and the melt index is 5g/10 min. The antioxidant is formed by mixing an antioxidant 1010 and an antioxidant 168 in a mass ratio of 2: 1.
In this example, the preparation method of the high melt strength polypropylene is as follows:
(1) the method comprises the steps of taking the polypropylene, the initiator, the vinyl acetate and the antioxidant according to the selected weight parts, uniformly mixing, and carrying out melt extrusion reaction by a double screw at the temperature of 160 ℃ and the screw rotating speed of 100rpm to obtain the vinyl acetate grafted polypropylene.
(2) Taking the vinyl acetate grafted polypropylene obtained in the step (1), the hyperbranched cross-linking agent and the antioxidant, and mixing the components in a ratio of 100: 5: 0.5, and performing melt extrusion reaction by a double screw at the temperature of 180 ℃ and the screw rotating speed of 200rpm to obtain the high melt strength polypropylene.
In the step (2), the antioxidant is formed by mixing an antioxidant 1010 and an antioxidant 168 in a mass ratio of 2: 1.
Example 3
The hyperbranched cross-linking agent of the embodiment is obtained by reacting diamine with polybasic acid. Wherein the diamine is hexamethylene diamine; the polybasic acid is ethylenediamine tetraacetic acid. The molecular weight of the hyperbranched cross-linking agent is 4500.
In this embodiment, the preparation method of the hyperbranched cross-linking agent is as follows: according to the weight portion, 50 portions of diamine and 50 portions of polybasic acid are taken, 0.1 portion of triethylamine is added as a catalyst, and the mixture reacts for 30min under mechanical stirring at the temperature of 120 ℃ and the pressure of 101KPa, so that the obtained compound with the hyperbranched structure is the hyperbranched cross-linking agent, and the main group on the surface is amino.
In this embodiment, the hyperbranched cross-linking agent is used to prepare high melt strength polypropylene, which is obtained by a synthetic reaction between vinyl acetate grafted polypropylene and the hyperbranched cross-linking agent in a twin-screw extrusion process.
The vinyl acetate grafted polypropylene is prepared from the following raw materials in parts by weight: 100 parts of polypropylene, 0.02 part of the initiator, 2 parts of vinyl acetate and 0.2 part of antioxidant.
Wherein the initiator is Benzoyl Peroxide (BPO). The polypropylene is copolymerized straight-chain polypropylene powder, and the melt index is 3.0g/10 min. The antioxidant is formed by mixing an antioxidant 1010 and an antioxidant 168 in a mass ratio of 2: 1.
In this example, the preparation method of the high melt strength polypropylene is as follows:
(1) the method comprises the steps of taking the polypropylene, the initiator, the vinyl acetate and the antioxidant according to the selected weight parts, uniformly mixing, and carrying out melt extrusion reaction by a double screw at the temperature of 180 ℃ and the screw rotating speed of 300rpm to obtain the vinyl acetate grafted polypropylene.
(2) Taking the vinyl acetate grafted polypropylene obtained in the step (1), the hyperbranched cross-linking agent and the antioxidant, and mixing the components in a ratio of 100: 3: 0.2, and performing melt extrusion reaction by a double screw at the temperature of 160 ℃ and the screw rotating speed of 100rpm to obtain the high melt strength polypropylene.
In the step (2), the antioxidant is formed by mixing an antioxidant 1010 and an antioxidant 168 in a mass ratio of 2: 1.
Example 4
The hyperbranched cross-linking agent of the embodiment is obtained by reacting diamine and polybasic acid. Wherein the diamine is formed by mixing ethylenediamine, methylpentamethylenediamine and hexamethylenediamine according to the weight ratio of 1:1: 2; the polybasic acid is prepared by mixing citric acid, butanetetracarboxylic acid and ethylenediamine tetraacetic acid according to the weight ratio of 1:3: 2. The molecular weight of the hyperbranched cross-linking agent is 4800.
In this embodiment, the preparation method of the hyperbranched cross-linking agent is as follows: according to the weight portion, 50 portions of diamine and 50 portions of polybasic acid are taken, 0.1 portion of triethylamine is added as a catalyst, and the mixture reacts for 30min under mechanical stirring at the temperature of 120 ℃ and the pressure of 101KPa, so that the obtained compound with the hyperbranched structure is the hyperbranched cross-linking agent, and the main group on the surface is amino.
In this embodiment, the hyperbranched cross-linking agent is used to prepare high melt strength polypropylene, which is obtained by a synthetic reaction between vinyl acetate grafted polypropylene and the hyperbranched cross-linking agent in a twin-screw extrusion process.
The vinyl acetate grafted polypropylene is prepared from the following raw materials in parts by weight: 100 parts of polypropylene, 0.02 part of the initiator, 2 parts of vinyl acetate and 0.2 part of antioxidant.
Wherein the initiator is Benzoyl Peroxide (BPO). The polypropylene is homopolymerized straight-chain polypropylene powder, and the melt index is 3g/10 min. The antioxidant is prepared by mixing an antioxidant 1010 and an antioxidant 168 according to a mass ratio of 2: 1.
In this example, the preparation method of the high melt strength polypropylene is as follows:
(1) the method comprises the steps of taking the polypropylene, the initiator, the vinyl acetate and the antioxidant according to the selected weight parts, uniformly mixing, and carrying out melt extrusion reaction by a double screw at the temperature of 180 ℃ and the screw rotating speed of 300rpm to obtain the vinyl acetate grafted polypropylene.
(2) Taking the vinyl acetate grafted polypropylene obtained in the step (1), the hyperbranched cross-linking agent and the antioxidant, and mixing the components in a ratio of 100: 0.5: 0.2, and performing melt extrusion reaction by a double screw at the temperature of 160 ℃ and the screw rotating speed of 100rpm to obtain the high melt strength polypropylene.
In the step (2), the antioxidant is formed by mixing an antioxidant 1010 and an antioxidant 168 in a mass ratio of 2: 1.
Comparative example 1
The process for producing polypropylene in this comparative example comprises the steps of:
taking the copolymerized straight-chain polypropylene powder with the melt index of 3.0g/10min, and carrying out melt extrusion by a double screw at the temperature of 160 ℃ and the screw rotating speed of 100 rpm.
Comparative example 2
The preparation method of polypropylene in the comparative example, which adopts the hyperbranched cross-linking agent obtained in example 3, comprises the following steps:
taking copolymerized linear polypropylene powder with the melt index of 3.0g/10min, a hyperbranched cross-linking agent and an antioxidant, and mixing the components in a proportion of 100: 3: 0.2, and carrying out melt extrusion reaction at a temperature of 160 ℃ and a screw rotating speed of 100rpm by a double screw.
Wherein the antioxidant is prepared by mixing an antioxidant 1010 and an antioxidant 168 in a mass ratio of 2: 1.
Comparative example of Effect
In order to verify the technical effects of the hyperbranched cross-linking agent and the high melt strength polypropylene, the following tests were carried out:
the melt strength of the high melt strength polypropylene or polypropylene prepared in examples 1 to 4 and comparative examples 1 to 2 was measured as follows: the measurements were made using a melt strength tester, which was a uniaxial draw of the polymer melt, first extruding the melt down the die of the extruder and simultaneously pulling it by two opposing rollers mounted on a balance beam. The force to which the melt strand is drawn is the uniform acceleration of the roller until the melt strand breaks, which is defined as the "melt strength".
Testing a melt index (i.e., melt index) with a melt index tester; testing the gel content according to the method of GB/T3682-2000; testing the tensile strength according to the method of GB/T2412-2008; testing the flexural modulus according to the method of GB/T9341-2008; the notched impact strength was tested according to the method of GB/T1843-2008.
The results of the experiment are as follows:
from the above results, it is understood that the high melt strength polypropylene of the present invention has good mechanical properties and processability, and does not generate gel. As can be seen from the comparison of comparative example 2 with comparative example 1, the hyperbranched cross-linking agent of the present invention can only improve the melt strength to a certain extent when applied to polypropylene that is not grafted with vinyl acetate. Comparison between comparative example 2 and examples 1-4 shows that the material obtained by reacting the hyperbranched cross-linking agent of the present invention with the vinyl acetate grafted polypropylene has significantly improved melt strength. In particular, the high melt strength polypropylene obtained in example 3 has the most outstanding properties in the high melt strength polypropylene with a long chain branched structure.
It will be appreciated by those skilled in the art that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The embodiments disclosed above are therefore to be considered in all respects as illustrative and not restrictive. All changes which come within the scope of or are equivalent to the scope of the invention are intended to be embraced therein.
Claims (10)
1. A hyperbranched cross-linking agent is characterized by being obtained by reacting diamine with polybasic acid.
2. The hyperbranched cross-linking agent of claim 1, wherein the diamine is at least one of ethylenediamine, methylpentamethylenediamine, and hexamethylenediamine;
the polybasic acid is at least one of citric acid, butanetetracarboxylic acid and ethylenediamine tetraacetic acid.
3. The hyperbranched cross-linking agent of claim 1, wherein the molecular weight of the hyperbranched cross-linking agent is 1000-8000.
4. A preparation method of a hyperbranched cross-linking agent is characterized by comprising the following steps:
taking diamine and polybasic acid, and reacting at 50-120 deg.C and 20-101KPa for 30-600min to obtain the final product;
optionally, the reaction is carried out under catalyst conditions, the catalyst being triethylamine.
5. A high melt strength polypropylene obtained by a synthesis reaction of polypropylene with the hyperbranched crosslinking agent of any one of claims 1 to 3.
6. The high melt strength polypropylene of claim 5, wherein the polypropylene is vinyl acetate grafted polypropylene.
7. The high melt strength polypropylene of claim 6, wherein the vinyl acetate grafted polypropylene is prepared from the following raw materials in parts by weight: 100 parts of polypropylene, 0.02-0.3 part of initiator, 0.5-3 parts of vinyl acetate and 0.2-1 part of antioxidant.
8. The high melt strength polypropylene of claim 7, wherein the initiator is at least one of t-butyl hydroperoxide, dicumyl peroxide, and benzoyl peroxide.
9. The preparation method of the polypropylene with high melt strength is characterized by comprising the following steps: the polypropylene and the hyperbranched cross-linking agent are uniformly mixed, and the high melt strength polypropylene is obtained through the twin-screw melt extrusion reaction at the temperature of 160 ℃ and the rotational speed of the screw of 100 ℃ and the rotational speed of 400 rpm.
10. The method of claim 9, wherein the polypropylene is vinyl acetate grafted polypropylene, and the preparation of the vinyl acetate grafted polypropylene comprises the following steps: the polypropylene, the initiator, the vinyl acetate and the antioxidant are uniformly mixed, and the vinyl acetate grafted polypropylene is obtained through a twin-screw melt extrusion reaction at the temperature of 160-200 ℃ and the screw rotation speed of 100-400 rpm.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109749235A (en) * | 2018-12-19 | 2019-05-14 | 万华化学集团股份有限公司 | Reversible micro- cross-linked dystectic strength polypropylene of one kind and preparation method thereof |
| CN111363143A (en) * | 2020-04-08 | 2020-07-03 | 武汉超支化树脂科技有限公司 | Hyperbranched polyamide for high-temperature nylon processing and preparation method and application thereof |
| CN113980300A (en) * | 2021-10-15 | 2022-01-28 | 中化石化销售有限公司 | Polypropylene with low gel content and high melt strength, preparation method and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109749235A (en) * | 2018-12-19 | 2019-05-14 | 万华化学集团股份有限公司 | Reversible micro- cross-linked dystectic strength polypropylene of one kind and preparation method thereof |
| CN111363143A (en) * | 2020-04-08 | 2020-07-03 | 武汉超支化树脂科技有限公司 | Hyperbranched polyamide for high-temperature nylon processing and preparation method and application thereof |
| CN113980300A (en) * | 2021-10-15 | 2022-01-28 | 中化石化销售有限公司 | Polypropylene with low gel content and high melt strength, preparation method and application thereof |
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| Title |
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