CN115895109A - Polypropylene composite material capable of being foamed repeatedly and preparation method and application thereof - Google Patents
Polypropylene composite material capable of being foamed repeatedly and preparation method and application thereof Download PDFInfo
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- -1 Polypropylene Polymers 0.000 title claims abstract description 132
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 123
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 119
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 50
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 50
- 239000003822 epoxy resin Substances 0.000 claims abstract description 36
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 36
- 239000000155 melt Substances 0.000 claims abstract description 20
- 229920005989 resin Polymers 0.000 claims abstract description 11
- 239000011347 resin Substances 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 8
- 239000004088 foaming agent Substances 0.000 claims abstract description 6
- 239000004593 Epoxy Substances 0.000 claims description 15
- 238000012360 testing method Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000003242 anti bacterial agent Substances 0.000 claims description 7
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- 239000004604 Blowing Agent Substances 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- 239000004156 Azodicarbonamide Substances 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 3
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 150000007970 thio esters Chemical class 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 2
- 235000013824 polyphenols Nutrition 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims 1
- 239000002530 phenolic antioxidant Substances 0.000 claims 1
- 150000008301 phosphite esters Chemical class 0.000 claims 1
- 238000000071 blow moulding Methods 0.000 abstract description 23
- 239000000463 material Substances 0.000 abstract description 22
- 238000005187 foaming Methods 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 5
- 239000010408 film Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 238000002844 melting Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 238000009423 ventilation Methods 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 241001391944 Commicarpus scandens Species 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000004599 antimicrobial Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 238000007665 sagging Methods 0.000 description 2
- 238000005482 strain hardening Methods 0.000 description 2
- 101100072645 Arabidopsis thaliana IPS3 gene Proteins 0.000 description 1
- 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 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 239000000945 filler Substances 0.000 description 1
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- 239000002861 polymer material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- HPOKESDSMZRZLC-UHFFFAOYSA-N propan-2-one;hydrochloride Chemical compound Cl.CC(C)=O HPOKESDSMZRZLC-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
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Abstract
The invention provides a polypropylene composite material capable of being foamed repeatedly, and a preparation method and application thereof. The polypropylene composite material comprises the following components in parts by weight: 100 parts of polypropylene resin, 1-2 parts of antioxidant, 0.5-1 part of antioxidant synergist, 2-5 parts of foaming agent and 0-0.5 part of other additives, wherein the polypropylene resin consists of low-melt-index linear polypropylene with the melt mass flow rate of 0.3-1.3 g/10min and high-melt-strength branched polypropylene with the melt strength of 36-60 cN; the antioxidant synergist is epoxy resin. The invention adopts the high melt strength polypropylene and the low melt strength polypropylene as the matrixes to ensure the blow molding processability of the polypropylene material, and simultaneously adds the epoxy resin as the antioxidant synergist into the antioxidant system to reduce the activity of free radicals in a polypropylene chain segment, so that the polypropylene still has good foaming performance after multiple blow molding processing.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a polypropylene composite material capable of being repeatedly foamed, and a preparation method and application thereof.
Background
Polypropylene (PP for short) has the advantages of good mechanical properties, easy molding and processing, low cost, etc., and is one of four general materials, and meanwhile, the Polypropylene material has the properties of being recyclable and degradable and is widely applied.
Blow molding is a common method for processing polypropylene resin, and a lightweight, sound-insulating and heat-insulating pipe can be prepared by foaming in the blow molding process and is used in the fields of automobile warm air pipes and the like. When the foaming polypropylene material is prepared by adopting a blow molding process, the polypropylene material is required to have good anti-sagging performance, for example, chinese patent CN108641194A discloses a hollow blow molding micro-foaming toolbox material, and the effects of good anti-sagging performance and no melt fracture when the wall thickness is optimally regulated and controlled can be achieved by adopting a high-melting index and low-melting index hybrid compound elastomer as a regulator.
However, in the blow molding process, a large amount of leftover materials are generated by the subsequent cutting process, and at present, the performance of the leftover materials in blowing and foaming is poor, and the leftover materials are usually recycled for other treatment, so that the utilization rate of raw materials of the foamed polypropylene composite material is low. Therefore, in order to further improve the utilization rate of the raw materials of the foamed polypropylene composite, it is necessary to provide a polypropylene composite which can be foamed repeatedly.
Disclosure of Invention
The invention aims to provide a polypropylene composite material capable of being repeatedly foamed in order to improve the utilization rate of raw materials of the foamed polypropylene composite material. The invention adopts the branched polypropylene with high melt strength and the linear polypropylene with low melt index as the matrix, has good blow-molding property, higher melt strength and better foaming property, improves the antioxidant system, and adds the Epoxy resin (EP for short) as the antioxidant synergist to improve the thermal stability of the polypropylene and reduce the processing degradation, so that the polypropylene composite material can be processed by repeated blow molding.
Another object of the present invention is to provide a method for preparing the polypropylene composite material capable of being repeatedly foamed.
The invention also aims to provide application of the polypropylene composite material capable of being repeatedly foamed in preparation of automobile parts, waterproof building pipes, medical appliances or electronic products.
In order to achieve the purpose, the invention adopts the following technical scheme:
a polypropylene composite material capable of being repeatedly foamed comprises the following components in parts by weight:
wherein the polypropylene resin consists of low-melt-index linear polypropylene with the melt mass flow rate of 0.3-1.3 g/10min and high-melt-strength branched polypropylene with the melt strength of 36-60 cN, the test conditions of the melt mass flow rate are 230 ℃ and 2.16kg, and the test conditions of the melt strength are 190 ℃; the antioxidant synergist is epoxy resin.
In the invention, the melt mass flow rate of the polypropylene is obtained by testing according to a method described in the GB/T3682.1-2018 standard; the melt strength of the polypropylene is obtained by testing with a melt strength tester.
The invention adopts the branched polypropylene with high melt strength and the linear polypropylene with low melting index to be matched as the matrix, thereby having good blowing plasticity, higher melt strength and better foaming performance, and simultaneously improving the antioxidant system. The epoxy group in the epoxy resin can act synergistically with the antioxidant to reduce the activity of free radicals in the polypropylene chain segment and slow down the degradation of the polypropylene.
Preferably, the epoxy value of the epoxy resin is 0.1-0.2 mol/100g, and the epoxy value is obtained by referring to a hydrochloric acid-acetone method test in GB/T1677-2008. The increase of the epoxy value in the epoxy resin can gradually improve the thermal stability and the repeated processability of the obtained polypropylene composite material, but when the epoxy value is increased to a certain amount, the compatibility of the epoxy group with stronger polarity in the epoxy resin and the nonpolar polypropylene is deteriorated, the dispersibility of the epoxy resin in the polypropylene material is deteriorated, and further, the melt strength of the polypropylene material in the blow molding process is reduced, and the film fracture occurs.
Preferably, the epoxy resin is at least one of a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a polyphenol type glycidyl ether epoxy resin, an aliphatic glycidyl ether epoxy resin, or a glycidyl ester type epoxy resin, and more preferably a bisphenol a type epoxy resin.
Preferably, the weight ratio of the low-melting linear polypropylene to the high-melting strength branched polypropylene is (0.8-3): 1. the low melting point means that the linear polypropylene accounts for too high, the strain hardening phenomenon of the material is weakened, the cells are easy to break, the stability and growth of the cells are not facilitated, and the cells are difficult to foam; low melt means that the polypropylene fraction is too low to have good flowability, but the melt strength decreases during the blowing process, and the thinner portion of the film is easily broken during the blowing process, and a complete thinner film cannot be produced.
Preferably, the antioxidant comprises a main antioxidant and an auxiliary antioxidant, and the main antioxidant is at least one of an amine antioxidant or a phenol antioxidant; the auxiliary antioxidant is at least one of phosphite antioxidant or thioester antioxidant.
Preferably, the weight ratio of the main antioxidant to the auxiliary antioxidant is (1-1.5): 1.
conventional blowing agents including, but not limited to, at least one of sodium bicarbonate, azodicarbonamide, or azobisisobutyronitrile may be used in the present invention.
Other additives, such as antimicrobial agents, may also be added as desired. The antibacterial agent is an inorganic salt compound containing silver ions, and the inorganic salt antibacterial agent can also be used as a heterogeneous nucleation point of foam pores to promote the foaming of the polypropylene material.
The preparation method of the polypropylene composite material capable of being repeatedly foamed comprises the following steps:
the polypropylene resin, the antioxidant synergist and other additives are uniformly mixed, melted and extruded at the temperature of 80-220 ℃, and then added with the foaming agent to be uniformly mixed to obtain the polypropylene composite material.
Preferably, the mixing is carried out in a high speed mixer.
Preferably, the melt extrusion is carried out in a twin-screw extruder in which the temperatures in the zones are: the temperature of the first zone is 80-120 ℃, the temperature of the second zone is 180-200 ℃, the temperature of the third zone is 180-220 ℃, the temperature of the fourth zone is 180-220 ℃, the temperature of the fifth zone is 180-220 ℃, the temperature of the sixth zone is 180-220 ℃, the temperature of the seventh zone is 180-220 ℃, the temperature of the eighth zone is 180-220 ℃, and the temperature of the ninth zone is 180-220 ℃; the length-diameter ratio of the screw of the double-screw extruder is 40; the rotating speed of the double-screw extruder is 400-450 r/min.
The application of the polypropylene composite material capable of being repeatedly foamed in the preparation of automobile parts, waterproof building pipes, medical instruments or electronic products is also within the protection scope of the invention. Preferably, the polypropylene composite material of the re-foamable foam is used for preparing a ventilation pipeline of an automobile air conditioner, a ventilation pipeline of a roof, a ventilation pipeline of an instrument panel, a defrosting pipe or a ventilation pipeline of a bottom of an automobile.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts the high melt strength branched polypropylene and the low melting index linear polypropylene as the matrix to ensure the blow molding processability of the polypropylene material, and simultaneously, the epoxy resin is added into the antioxidant system as the antioxidant synergist to reduce the activity of free radicals in the polypropylene chain segment, so that the polypropylene still has good foaming performance after multiple blow molding processing.
Detailed Description
The present invention will be further described with reference to specific examples for better illustrating the objects, technical solutions and advantages of the present invention, but the examples are not intended to limit the present invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated. Unless otherwise indicated, reagents and materials used in the present invention are commercially available.
The following raw materials are selected in the embodiment of the invention:
low melt means linear polypropylene:
PP-1: PP B8101, the melt mass flow rate of which is 0.3g/10min under the conditions of 230 ℃ and 2.16kg, purchased from Yanshan petrochemical;
PP-2: PP 3010, melt mass flow rate of 1.3g/10min at 230 ℃ under 2.16kg, purchased from Taiwan plastics industries, ltd;
high melt strength branched polypropylene:
and (3) PP-3: WB140 HMS, melt strength at 190 ℃ of 36cN, available from northern Europe chemical;
PP-4: PP 561P (HEX 17112) with a melt strength of 60cN at 190 ℃ available from Sauter basic industries;
antioxidant:
phenol type main antioxidant: antioxidant 1010 available from Sanfeng chemical Co., ltd, linyi, shandong province;
phosphite secondary antioxidant: antioxidant 168 available from Sanfeng chemical Co., ltd, linyi, shandong province;
thioester type secondary antioxidant: antioxidant RIANOX 412S available from Tianjin Li An Long New materials GmbH;
an antioxidant synergist:
EP-1: bisphenol A epoxy resin, jer 1004, epoxy value 0.1mol/100g, available from Shanghai Zhongsi industries, ltd;
EP-2: bisphenol a type epoxy resin, 5213B, with an epoxy value of 0.17mol/100g, available from the chemical industry of silosa;
EP-3: bisphenol A type epoxy resin, KD-211G, epoxy value of 0.2mol/100G, purchased from Kyowa chemical;
EP-4: bisphenol A type epoxy resin, KD-211SW, epoxy value of 0.23mol/100g, purchased from Kyowa chemical;
EP-5: bisphenol A epoxy resin, jer1007, with an epoxy value of 0.05mol/100g, available from Shanghai Zhongsi industries, ltd;
EP-6: bisphenol F type epoxy resin, jer4005P, epoxy value of 0.1mol/100g, available from Shanghai Zhongsi industries Co., ltd;
EP-7: aliphatic glycidyl ether epoxy resin, YL7410, epoxy equivalent 0.19mol/100g, available from Shanghai Zhongsi industries, inc.;
foaming agent:
sodium bicarbonate (NaHCO) 3 ): f-70 available from Yonghe and Fine chemical industries (Normal ripening) Ltd;
azodicarbonamide blowing agents (AC blowing agents), LD703S, available from New materials GmbH, shangjie, zhejiang;
other additives:
antibacterial agents: inorganic salt phosphate-supported silver ion antibacterial agent, IONPURE IPS3, available from Beijing Ai Sier technology Limited;
in the present invention, the other additives (e.g., antimicrobial agents) are the same substances in the parallel test.
Examples 1 to 18
The embodiment of the invention provides a series of polypropylene composite materials capable of being repeatedly foamed, which are prepared according to a preparation method comprising the following steps:
according to the formula in the table 1-2, firstly adding the polypropylene resin, the antioxidant synergist and other additives into a high-speed mixer, uniformly mixing, feeding into a double-screw extruder (the length-diameter ratio of a screw is 40.
TABLE 1 component formulation (parts by weight) of the polypropylene composites of examples 1 to 9
TABLE 2 raw material formulation (parts by weight) of the polypropylene composites of examples 10 to 18
Comparative example 1
This comparative example provides a polypropylene composite material prepared according to the preparation method of example 1, which is different from example 1 in that the low-melt-index linear polypropylene PP-1 is replaced with the high-melt-strength branched polypropylene PP-3, and other raw materials and amounts are unchanged, i.e., only the high-melt-strength branched polypropylene is contained in the polypropylene resin.
Comparative example 2
This comparative example provides a polypropylene composite material prepared according to the preparation method of example 1, which is different from example 1 in that the high melt strength branched polypropylene PP-3 is replaced with the low melt index linear polypropylene PP-1, and other raw materials and amounts are unchanged, that is, only the low melt index linear polypropylene is included in the polypropylene resin.
Comparative example 3
This comparative example provides a polypropylene composite prepared according to the method of example 1, differing from example 1 in that no epoxy resin EP-1 is added.
Comparative example 4
This comparative example provides a polypropylene composite prepared according to the method of example 1, except that no antioxidant is added as in example 1.
Performance test
The properties of the polypropylene composite materials obtained in the above examples and comparative examples are characterized, and the specific test items, test methods and results are as follows:
1. density (g/mL): the polypropylene composite materials prepared in the above examples and comparative examples are blown into films, the films are obtained by testing according to the method A described in the standard GB/T1033-1986, the prepared films are blown again, and the density of the films obtained by the 4 th blow molding is tested, and the specific test results are shown in the table 3;
2. thickness test of polypropylene films: the thickness (mm) of the polypropylene film obtained by blow molding the polypropylene composite material prepared in the above examples and comparative examples and the thickness of the film obtained by blow molding at the 4 th time under the same blow molding process conditions were measured by using a thickness measuring instrument, the thickness of the present invention was an average thickness, five-point sampling method was used to measure the thickness of five points on the film, and finally the average thickness of five points and the variance thereof were taken as test results, which are detailed in table 3;
table 3 results of performance testing
From the above results, it can be seen that:
the polypropylene composite material capable of being repeatedly foamed prepared by the embodiments of the invention has good repeated blow molding processability, and can still keep good processability and foaming performance after being processed for many times.
The results of example 1 and examples 6-9 show that the polypropylene, the antioxidant and the foaming agent selected by the invention can be used for preparing the polypropylene composite material with good repeated blow molding and repeated foaming performances.
The results of example 1 and examples 10 to 13 show that the thermal stability and the repeated processability of the obtained polypropylene composite material are gradually improved with the increase of the epoxy value in the epoxy resin, but when the epoxy value is increased to a certain amount, the compatibility between the epoxy group with stronger polarity in the epoxy resin and the non-polar polypropylene is deteriorated, the dispersibility of the epoxy resin in the polypropylene material is deteriorated, and further, the melt strength of the polypropylene material in the blow molding process is reduced, and the film fracture may occur.
The results of examples 1 to 5 show that as the ratio of the low-melting linear polypropylene in the polypropylene matrix increases, the melt strength of the polypropylene material becomes higher, which is advantageous for the blow molding production of a thin film with uniform thickness, but the cells tend to break during the foaming process, the density of the obtained polypropylene film gradually increases, and the foaming effect becomes worse. Therefore, by combining the two properties, the polypropylene composite material with better performance of repeated blow molding and repeated foaming can be prepared within the proportion range of the invention. In the comparative example 1, only the high melt strength branched polypropylene is added, although the high melt strength branched polypropylene has good fluidity and is beneficial to foaming, in the blow molding process, a thin part is easy to break, a complete thin polypropylene film cannot be prepared, and the thickness of a film forming part is also large; in the polypropylene of comparative example 2, only low-melting polypropylene was added, the flowability of the polypropylene resin matrix was too poor, the filler dispersion was not uniform, the strain hardening phenomenon of the material was weak, the cells were easily broken, the cell stabilization and growth were not facilitated, and the blow molding foaming could not be performed.
The results of comparative examples 3 and 4 show that, if any one of the antioxidant and the epoxy resin is absent, the performance of the obtained polypropylene product can be obviously reduced after the obtained polypropylene composite material is repeatedly processed for many times, and the antioxidant and the epoxy resin have synergistic effect, so that the activity of free radicals in a polypropylene chain segment can be obviously reduced, and the degradation of polypropylene can be slowed down.
The results of example 1 and examples 16 to 18 show that the influence of the antioxidant, the antioxidant synergist, the foaming agent and the antibacterial agent in the dosage ranges on the performance of the obtained polypropylene composite material is less than the influence of the epoxy value of the polypropylene matrix and the antioxidant synergist on the foaming performance and repeated foaming performance of the material.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A polypropylene composite material capable of being repeatedly foamed is characterized by comprising the following components in parts by weight:
wherein the polypropylene resin consists of low-melt-index linear polypropylene with the melt mass flow rate of 0.3-1.3 g/10min and high-melt-strength branched polypropylene with the melt strength of 36-60 cN, the test conditions of the melt mass flow rate are 230 ℃ and 2.16kg, and the test conditions of the melt strength are 190 ℃; the antioxidant synergist is epoxy resin.
2. The re-foamable polypropylene composite according to claim 1, wherein the epoxy value of the epoxy resin is 0.1 to 0.2mol/100g.
3. The re-foamable polypropylene composite of any one of claims 1 or 2, wherein the epoxy resin is at least one of a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a polyphenol type glycidyl ether epoxy resin, an aliphatic glycidyl ether epoxy resin, or a glycidyl ester type epoxy resin.
4. The re-foamable polypropylene composite according to claim 1, wherein the weight ratio of the low-melt-index linear polypropylene to the high-melt-strength branched polypropylene is (0.8 to 3): 1.
5. the re-foamable polypropylene composite of claim 1, wherein the antioxidant comprises a primary antioxidant and a secondary antioxidant, the primary antioxidant being at least one of an amine antioxidant or a phenolic antioxidant; the auxiliary antioxidant is at least one of phosphite ester antioxidant or thioester antioxidant.
6. The re-foamable polypropylene composite according to claim 5, wherein the weight ratio of the primary antioxidant to the secondary antioxidant is (1-1.5): 1.
7. the re-foamable polypropylene composite of claim 1, wherein the blowing agent is at least one of sodium bicarbonate, azodicarbonamide, or azobisisobutyronitrile.
8. The re-foamable polypropylene composite material according to claim 1, wherein the other additive is an antibacterial agent, and the antibacterial agent is an inorganic salt compound containing silver ions.
9. A process for the preparation of a re-foamable polypropylene composite according to any one of claims 1 to 8, comprising the steps of:
the polypropylene resin, the antioxidant synergist and other additives are uniformly mixed, melted and extruded at the temperature of 80-220 ℃, and then added with the foaming agent to be uniformly mixed to obtain the polypropylene composite material.
10. Use of the re-foamable polypropylene composite according to any one of claims 1 to 8 for the manufacture of automotive parts, waterproof building pipes, medical devices or electronic products.
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| CN202211391111.0A CN115895109B (en) | 2022-11-08 | 2022-11-08 | Polypropylene composite material capable of being repeatedly foamed and preparation method and application thereof |
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| CN202211391111.0A CN115895109B (en) | 2022-11-08 | 2022-11-08 | Polypropylene composite material capable of being repeatedly foamed and preparation method and application thereof |
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| CN115895109A true CN115895109A (en) | 2023-04-04 |
| CN115895109B CN115895109B (en) | 2024-05-10 |
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| CN202211391111.0A Active CN115895109B (en) | 2022-11-08 | 2022-11-08 | Polypropylene composite material capable of being repeatedly foamed and preparation method and application thereof |
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Citations (3)
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| CN104987590A (en) * | 2015-07-06 | 2015-10-21 | 安徽成方新材料科技有限公司 | Environment-friendly recyclable foamed polypropylene and macromolecule absorbent composite material and preparation method thereof |
| CN110218418A (en) * | 2019-06-26 | 2019-09-10 | 美瑞新材料股份有限公司 | A kind of lightweight epoxy resin composite material, preparation method and application |
| CN112126150A (en) * | 2020-09-27 | 2020-12-25 | 上海交通大学 | Recyclable POE vitrimer elastomer, foaming material, and preparation methods and applications thereof |
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| CN104987590A (en) * | 2015-07-06 | 2015-10-21 | 安徽成方新材料科技有限公司 | Environment-friendly recyclable foamed polypropylene and macromolecule absorbent composite material and preparation method thereof |
| CN110218418A (en) * | 2019-06-26 | 2019-09-10 | 美瑞新材料股份有限公司 | A kind of lightweight epoxy resin composite material, preparation method and application |
| CN112126150A (en) * | 2020-09-27 | 2020-12-25 | 上海交通大学 | Recyclable POE vitrimer elastomer, foaming material, and preparation methods and applications thereof |
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| 高萍;王醴均;蒋团辉;龚维;何力;: "EP含量对PP/PP-g-MAH/EP微孔发泡复合材料发泡行为及力学性能的影响", 高分子材料科学与工程, no. 01 * |
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