CN115895109B - Polypropylene composite material capable of being repeatedly foamed and preparation method and application thereof - Google Patents
Polypropylene composite material capable of being repeatedly foamed and preparation method and application thereof Download PDFInfo
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- -1 Polypropylene Polymers 0.000 title claims abstract description 135
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 127
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 127
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 50
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 48
- 239000003822 epoxy resin Substances 0.000 claims abstract description 38
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 38
- 239000000155 melt Substances 0.000 claims abstract description 20
- 229920005989 resin Polymers 0.000 claims abstract description 13
- 239000011347 resin Substances 0.000 claims abstract description 13
- 239000000654 additive Substances 0.000 claims abstract description 8
- 239000004088 foaming agent Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 15
- 239000004593 Epoxy Substances 0.000 claims description 14
- 238000012360 testing method Methods 0.000 claims description 14
- 239000003242 anti bacterial agent Substances 0.000 claims description 6
- 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
- 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
- 238000001125 extrusion Methods 0.000 claims description 3
- 235000013824 polyphenols Nutrition 0.000 claims description 3
- 150000007970 thio esters Chemical class 0.000 claims description 3
- 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 2
- 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
- 238000010276 construction Methods 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 150000008442 polyphenolic compounds Chemical class 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
- 238000005187 foaming Methods 0.000 abstract description 23
- 239000000463 material Substances 0.000 abstract description 20
- 238000000071 blow moulding Methods 0.000 abstract description 19
- 239000011159 matrix material Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 14
- 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 10
- 238000007664 blowing Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- 241001391944 Commicarpus scandens Species 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000009423 ventilation Methods 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 3
- 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
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000007665 sagging Methods 0.000 description 2
- 238000005482 strain hardening Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 101100072645 Arabidopsis thaliana IPS3 gene Proteins 0.000 description 1
- 229910019142 PO4 Inorganic materials 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
- 238000004378 air conditioning Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002861 polymer 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
- 238000004064 recycling Methods 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
- 238000010998 test method Methods 0.000 description 1
- 238000011282 treatment Methods 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 repeatedly foamed, 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 matrix to ensure the blow molding processability of the polypropylene material, and simultaneously, the epoxy resin is added into the antioxidant system to serve as an antioxidant synergist, thereby reducing the activity of free radicals in the polypropylene chain segment and ensuring that the polypropylene still has good foaming performance after the polypropylene is subjected to blow molding processing for many times.
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, a preparation method and application thereof.
Background
Polypropylene (PP) has the advantages of good mechanical properties, easy molding and processing, low cost and the like, and is one of four general materials, and meanwhile, the Polypropylene material has the properties of recycling and degradability and is widely applied.
Blow molding is a common method for processing polypropylene resin, and light, sound and heat insulation pipes can be prepared by foaming in the blow molding process, and the method 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 tool box material, and the effect that the anti-sagging performance is good and the melt is not broken during the optimized regulation and control of the wall thickness can be achieved by adopting a high melt index and low melt index hybrid compound elastomer as a regulator.
However, in the blow molding process, a large amount of leftover materials are generated in the subsequent cutting process, and the performance of re-blowing and foaming of the leftover materials is poor at present, and the leftover materials are usually recycled for other treatments, so that the raw material utilization rate of the foamed polypropylene composite material is low. Therefore, in order to further increase the raw material utilization of the foamed polypropylene composite, it is desirable to provide a polypropylene composite that can be repeatedly foamed.
Disclosure of Invention
The invention aims to provide a repeatable foaming polypropylene composite material in order to improve the raw material utilization rate of the foaming polypropylene composite material. The invention adopts the matching of the branched polypropylene with high melt strength and the linear polypropylene with low melt index as a matrix, has good blowing plasticity, higher melt strength and better foaming performance, improves an antioxidant system, and adds Epoxy resin (EP for short) as an antioxidant synergist, thereby improving the thermal stability of polypropylene, reducing processing degradation and enabling the polypropylene composite material to be subjected to repeated blowing processing.
It is another object of the present invention to provide a method for preparing the re-foamable polypropylene composite.
Another object of the present invention is to provide the use of the re-foamable polypropylene composite material for the preparation of automotive parts, construction waterproof tubing, medical devices or electronic products.
In order to achieve the above purpose, the invention adopts the following technical scheme:
A re-foamable polypropylene composite comprising the following components in parts by weight:
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, wherein the test condition of the melt mass flow rate is 230 ℃ and 2.16kg, and the test condition of the melt strength is 190 ℃; the antioxidant synergist is epoxy resin.
In the invention, the melt mass flow rate of polypropylene is obtained by testing by a method described in a reference standard GB/T3682.1-2018; the melt strength of polypropylene is obtained by testing with a melt strength measuring instrument.
The invention adopts the branched polypropylene with high melt strength and the linear polypropylene with low melt strength as the matrix, has good blowing plasticity, higher melt strength and better foaming performance, improves an antioxidant system, and can improve the heat stability of the polypropylene, reduce processing degradation, ensure that the polypropylene composite material can be repeatedly blown and processed, and still has good foaming performance after repeated processing for a plurality of times. The epoxy groups in the epoxy resin can cooperate with the antioxidant to reduce the activity of free radicals in the polypropylene chain segments and slow down the degradation of polypropylene.
Preferably, the epoxy resin has an epoxy value of 0.1 to 0.2mol/100g, which is tested with reference to the hydrochloric acid-acetone method described in standard 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 poor, the dispersibility of the epoxy resin in the polypropylene material is poor, the melt strength of the polypropylene material is further reduced in the blowing process, and the condition of film breakage occurs.
Preferably, the epoxy resin is at least one of bisphenol a type epoxy resin, bisphenol F type epoxy resin, polyphenol type glycidyl ether epoxy resin, aliphatic glycidyl ether epoxy resin, or glycidyl ester type epoxy resin, and more preferably bisphenol a type epoxy resin.
Preferably, the weight ratio of the low melt index linear polypropylene to the high melt strength branched polypropylene is (0.8-3): 1. the linear polypropylene with low melt index has a too high ratio, the strain hardening phenomenon of the material is weakened, the cells are easy to break, the stability and the growth of the cells are not facilitated, and the foaming is difficult; the low melt index polypropylene has a too low ratio, and has better fluidity, but the melt strength is reduced in the blowing process, and the thinner part of the film is easy to break in the blowing process, so that the complete thinner film cannot be prepared.
Preferably, the antioxidant comprises a primary antioxidant and a secondary antioxidant, and the primary 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 may be used in the present invention including, but not limited to, at least one of sodium bicarbonate, azodicarbonamide, or azodiisobutyronitrile.
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 heterogeneous nucleation points of cells to promote foaming of the polypropylene material.
The preparation method of the repeatedly foamable polypropylene composite material comprises the following steps:
uniformly mixing polypropylene resin, an antioxidant synergist and other additives, then carrying out melt extrusion at 80-220 ℃, and then adding a foaming agent and uniformly mixing to obtain the modified polypropylene resin.
Preferably, the mixing is performed in a high speed mixer.
Preferably, the melt extrusion is performed in a twin screw extruder, the temperatures of the zones in the twin screw extruder being respectively: the first area temperature is 80-120 ℃, the second area temperature is 180-200 ℃, the third area temperature is 180-220 ℃, the fourth area temperature is 180-220 ℃, the fifth area temperature is 180-220 ℃, the sixth area temperature is 180-220 ℃, the seventh area temperature is 180-220 ℃, the eighth area temperature is 180-220 ℃, and the ninth area temperature is 180-220 ℃; the length-diameter ratio of the screw of the double-screw extruder is 40:1; the rotating speed of the double-screw extruder is 400-450 r/min.
The application of the repeatedly foamable polypropylene composite material in preparing automobile parts, building waterproof pipes, medical appliances or electronic products is also within the protection scope of the invention. Preferably, the re-foamable polypropylene composite material is used for the preparation of automotive air conditioning ventilation ducts, roof ventilation ducts, instrument panel ventilation ducts, defrost ducts or underbody ventilation ducts.
Compared with the prior art, the invention has the beneficial effects that:
The invention adopts the high melt strength branched polypropylene and the low melt index linear polypropylene to match as the matrix to ensure the blow molding processability of the polypropylene material, and simultaneously, the epoxy resin is added into the antioxidant system to serve as the antioxidant synergist, thereby reducing the activity of free radicals in the polypropylene chain segment, and ensuring that the polypropylene still has good foaming performance after the polypropylene is subjected to blow molding processing for many times.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples, which are not intended to limit the present invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art. The reagents and materials used in the present invention are commercially available unless otherwise specified.
The following raw materials are selected in the embodiment of the invention:
Low melt index linear polypropylene:
PP-1: PP B8101, available from Yanshan petrochemical industry, has a melt mass flow rate of 0.3g/10min at 230℃under 2.16 kg;
PP-2: PP 3010, melt mass flow rate at 230℃and 2.16kg was 1.3g/10min, available from Taiwan plastics industries, inc.;
High melt strength branched polypropylene:
PP-3: WB140 HMS, melt strength at 190 ℃ of 36cN, available from northern european chemical;
PP-4: PP 561P (HEX 17112), melt strength at 190 ℃ of 60cN, commercially available from sauter basic industries;
An antioxidant:
Phenolic primary antioxidants: antioxidant 1010, available from Sanfeng chemical Co., ltd in Yi city, shandong province;
phosphite ester auxiliary antioxidant: antioxidant 168, available from Sanfeng chemical Co., ltd in Yi city, shandong province;
thioester auxiliary antioxidants: antioxidant RIANOX 412S, available from Tianjin An Long New Material Co., ltd;
antioxidant synergist:
EP-1: bisphenol A type epoxy resin, jer 1004, having an epoxy value of 0.1mol/100g, available from Shanghai Zhongsi Co., ltd;
EP-2: bisphenol A type epoxy resin, 5213B, epoxy value 0.17mol/100g, available from Injusa chemical;
EP-3: bisphenol A type epoxy resin, KD-211G, with epoxy value of 0.2mol/100G, purchased from national chemistry;
EP-4: bisphenol A type epoxy resin, KD-211SW, epoxy value of 0.23mol/100g, purchased from national chemistry;
EP-5: bisphenol A type epoxy resin, jer1007, having an epoxy value of 0.05mol/100g, available from Shanghai Zhongsi Utility Co., ltd;
EP-6: bisphenol F type epoxy resin, jer4005P, epoxy value of 0.1mol/100g, purchased from Shanghai Zhongsi Utility Co., ltd;
EP-7: aliphatic glycidyl ether epoxy resin, YL7410, epoxy equivalent of 0.19mol/100g, available from Shanghai Zhongsi Utility Co., ltd;
foaming agent:
Sodium bicarbonate (NaHCO 3): f-70, available from Yongand Fine chemical (frequent) Co., ltd;
azodicarbonamide blowing agent (AC blowing agent) LD703S, available from Zhejiang Jie Shangjie New Material Co., ltd;
other additives:
Antibacterial agent: inorganic salt phosphate-loaded silver ion antibacterial agent, IONPURE IPS3, purchased from Beijing Ai Sier technologies Co., ltd;
In the present invention, the other additives (e.g., antimicrobial agents) are the same in the parallel test.
Examples 1 to 18
The embodiment of the invention provides a series of repeatedly foamable polypropylene composite materials, which are prepared by a preparation method comprising the following steps:
According to the formula shown in tables 1-2, firstly adding polypropylene resin, an antioxidant synergist and other additives into a high-speed mixer, uniformly mixing, then feeding into a double-screw extruder (the length-diameter ratio of the screw is 40:1), feeding the mixture into a double-screw extruder, wherein the rotating speed of the screw is 450r/min, and uniformly mixing the mixture at 80-220 ℃ (wherein the temperature of each region in the double-screw extruder is respectively that the temperature of the first region is 80-120 ℃, the temperature of the second region is 180-200 ℃, the temperature of the third region is 180-220 ℃, the temperature of the fourth region is 180-220 ℃, the temperature of the fifth region is 180-220 ℃, the temperature of the sixth region is 180-220 ℃, the temperature of the seventh region is 180-220 ℃, the temperature of the eighth region is 180-220 ℃, and then adding a foaming agent, and uniformly mixing to obtain the repeatable foaming polypropylene composite material.
Table 1 the composition formulations (parts by weight) of the polypropylene composites of examples 1 to 9
Table 2 raw material formulations (parts by weight) of Polypropylene composite materials of examples 10 to 18
Comparative example 1
The comparative example provides a polypropylene composite material prepared according to the preparation method of example 1, which differs from example 1 in that the low melt index linear polypropylene PP-1 is replaced by the high melt strength branched polypropylene PP-3, and other raw materials and amounts are unchanged, i.e. the polypropylene resin only comprises the high melt strength branched polypropylene.
Comparative example 2
The comparative example provides a polypropylene composite material prepared according to the preparation method of example 1, which differs from example 1 in that the high melt strength branched polypropylene PP-3 is replaced by low melt index linear polypropylene PP-1, and other raw materials and amounts are unchanged, i.e. the polypropylene resin only comprises low melt index linear polypropylene.
Comparative example 3
This comparative example provides a polypropylene composite, prepared according to the preparation method of example 1, differing from example 1 in that no epoxy resin EP-1 was added.
Comparative example 4
This comparative example provides a polypropylene composite, prepared according to the method of example 1, except that no antioxidant was added to the polypropylene composite as in example 1.
Performance testing
The performance of the polypropylene composite materials obtained in the above examples and comparative examples was characterized, and specific test items, test methods and results were as follows:
1. Density (g/mL): the polypropylene composite materials prepared in the above examples and comparative examples were blown into films, which were obtained by the test described in the reference of the method A of the standard GB/T1033-1986, and the prepared films were re-blown, and the densities of the films obtained by the 4 th blow molding were tested, and the specific test results are shown in Table 3;
2. Thickness test of polypropylene film: the thickness (mm) of the polypropylene film obtained by blow molding the polypropylene composite materials prepared in the above examples and comparative examples and the thickness of the film obtained by blow molding the polypropylene composite materials for the 4 th time under the same blow molding process conditions were tested by a thickness measuring instrument, the thickness of the present invention is the average thickness, the thickness of five points is tested by a five-point sampling method on the film, and finally the average thickness of the five points and the variance thereof are taken as test results, and the test results are shown in table 3;
TABLE 3 Performance test results
From the above results, it can be seen that:
The repeatedly foamable polypropylene composite material prepared by the embodiments of the invention has good repeatedly blow molding processing performance, and still has good processing performance and foaming performance after repeated processing.
The results of example 1 and examples 6-9 show that polypropylene, an antioxidant and a foaming agent selected by the invention can be prepared into polypropylene composite materials with good performance of repeated blow molding and repeated foaming.
The results of examples 1 and 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 of the epoxy group with the nonpolar polypropylene in the epoxy resin is poor, the dispersibility of the epoxy resin in the polypropylene material is poor, the melt strength of the polypropylene material is reduced in the blowing process, and the situation of film breakage can occur.
The results of examples 1 to 5 show that as the ratio of the linear polypropylene with low melt index in the polypropylene matrix increases, the melt strength of the polypropylene material becomes high, which is advantageous for blow molding to obtain a film with uniform and thin thickness, but the cells have a tendency to break during the foaming process, and the density of the obtained polypropylene film gradually increases, and the foaming effect becomes poor. Therefore, by combining the two properties, the polypropylene composite material with good properties of repeated blow molding and repeated foaming can be prepared within the range of the proportion of the invention. In comparative example 1, only high melt strength branched polypropylene is added, and although the polypropylene has good fluidity and is favorable for foaming, in the blow molding process, the thinner part is easy to break, a complete thinner polypropylene film cannot be prepared, and the thickness of a film forming part is also larger; the polypropylene in comparative example 2 is only added with low melt index polypropylene, the fluidity of the polypropylene resin matrix is too poor, the filler is unevenly dispersed, 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 blow molding foaming cannot be carried out.
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 is obviously reduced after repeated processing for a plurality of times, and the antioxidant and the epoxy resin act synergistically, so that the activity of free radicals in the polypropylene chain segment can be obviously reduced, and the degradation of polypropylene is slowed down.
The results of examples 1 and 16 to 18 show that the antioxidant, the antioxidant synergist, the foaming agent and the antibacterial agent have less influence on the performance of the obtained polypropylene composite material than the influence of the epoxy value in the polypropylene matrix and the antioxidant synergist on the foaming performance and the repeated foaming performance of the material within the above dosage range.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (8)
1. A re-foamable polypropylene composite material, comprising the following components in parts by weight:
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, wherein the test condition of the melt mass flow rate is 230 ℃ and 2.16kg, and the test condition of the melt strength is 190 ℃; the weight ratio of the low melt index linear polypropylene to the high melt strength branched polypropylene is (0.8-3): 1, a step of; the antioxidant synergist is epoxy resin, and the epoxy value of the epoxy resin is 0.1-0.2 mol/100g.
2. The re-foamable polypropylene composite material according to claim 1, wherein the epoxy resin is at least one of bisphenol a type epoxy resin, bisphenol F type epoxy resin, polyphenol type glycidyl ether epoxy resin, aliphatic glycidyl ether epoxy resin, or glycidyl ester type epoxy resin.
3. The re-foamable polypropylene composite material 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 antioxidant or thioester antioxidant.
4. The re-foamable polypropylene composite material according to claim 3, wherein the weight ratio of the primary antioxidant and the secondary antioxidant is (1 to 1.5): 1.
5. The re-foamable polypropylene composite material according to claim 1, wherein the blowing agent is at least one of sodium bicarbonate, azodicarbonamide or azodiisobutyronitrile.
6. The re-foamable polypropylene composite material according to claim 1, wherein the other additive is an antibacterial agent which is an inorganic salt compound containing silver ions.
7. A process for the preparation of a re-foamable polypropylene composite material as defined in any one of claims 1 to 6, comprising the steps of:
uniformly mixing polypropylene resin, an antioxidant synergist and other additives, then carrying out melt extrusion at 80-220 ℃, and then adding a foaming agent and uniformly mixing to obtain the modified polypropylene resin.
8. Use of a re-foamable polypropylene composite material as defined in any one of claims 1 to 6 for the preparation of automotive parts, construction waterproof tubing, medical devices or electronic products.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (1)
| Title |
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| 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;高萍;王醴均;蒋团辉;龚维;何力;;高分子材料科学与工程(01) * |
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