CN117887170A - Composite auxiliary agent master batch special for polypropylene pipe and application thereof - Google Patents
Composite auxiliary agent master batch special for polypropylene pipe and application thereof Download PDFInfo
- Publication number
- CN117887170A CN117887170A CN202410135250.XA CN202410135250A CN117887170A CN 117887170 A CN117887170 A CN 117887170A CN 202410135250 A CN202410135250 A CN 202410135250A CN 117887170 A CN117887170 A CN 117887170A
- Authority
- CN
- China
- Prior art keywords
- polypropylene
- modified
- master batch
- antioxidant
- reinforcing agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 polypropylene Polymers 0.000 title claims abstract description 131
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 117
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 117
- 239000002131 composite material Substances 0.000 title claims abstract description 65
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 37
- 239000012752 auxiliary agent Substances 0.000 title claims abstract description 31
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical class [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 33
- 238000002360 preparation method Methods 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 32
- 229920002313 fluoropolymer Polymers 0.000 claims abstract description 29
- 239000004811 fluoropolymer Substances 0.000 claims abstract description 29
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 28
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 28
- 239000002667 nucleating agent Substances 0.000 claims abstract description 23
- 239000000314 lubricant Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000012744 reinforcing agent Substances 0.000 claims description 33
- 229960001545 hydrotalcite Drugs 0.000 claims description 26
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000004611 light stabiliser Substances 0.000 claims description 19
- 239000002033 PVDF binder Substances 0.000 claims description 17
- 150000007942 carboxylates Chemical class 0.000 claims description 17
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- 239000004596 additive masterbatch Substances 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 12
- 239000000155 melt Substances 0.000 claims description 11
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 8
- 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 claims description 7
- 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 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 claims description 5
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical group [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 5
- 235000013539 calcium stearate Nutrition 0.000 claims description 5
- 239000008116 calcium stearate Substances 0.000 claims description 5
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 4
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 3
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 claims description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001721 carbon Chemical class 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims description 2
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 claims description 2
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920002620 polyvinyl fluoride Polymers 0.000 claims description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 2
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 8
- 230000002706 hydrostatic effect Effects 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 7
- 230000006911 nucleation Effects 0.000 abstract description 6
- 238000010899 nucleation Methods 0.000 abstract description 6
- 238000005191 phase separation Methods 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract description 2
- 238000002844 melting Methods 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000012545 processing Methods 0.000 description 7
- BAVNDESSHRPRRF-UHFFFAOYSA-N ethenyl-diethyl-methylsilane Chemical compound CC[Si](C)(CC)C=C BAVNDESSHRPRRF-UHFFFAOYSA-N 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- CSJKPFQJIDMSGF-UHFFFAOYSA-K aluminum;tribenzoate Chemical compound [Al+3].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 CSJKPFQJIDMSGF-UHFFFAOYSA-K 0.000 description 2
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 2
- 235000010234 sodium benzoate Nutrition 0.000 description 2
- 239000004299 sodium benzoate Substances 0.000 description 2
- UPFSMSDGKQSRLD-UHFFFAOYSA-N 2-hexylpropanedioic acid Chemical compound CCCCCCC(C(O)=O)C(O)=O UPFSMSDGKQSRLD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- RKFMOTBTFHXWCM-UHFFFAOYSA-M [AlH2]O Chemical group [AlH2]O RKFMOTBTFHXWCM-UHFFFAOYSA-M 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Abstract
The invention discloses a composite auxiliary agent master batch special for polypropylene pipes, which comprises the following preparation raw materials in percentage by weight: 10-20% of composite nucleating agent, 5-20% of antioxidant I, 1-5% of lubricant and the balance of polypropylene. The invention adopts the combined action of the modified hydrotalcite and the modified fluoropolymer, improves the fluidity of the low-melt-index polypropylene material when the low-melt-index polypropylene material is applied to the pipe, optimizes the structural uniformity of polypropylene, and improves the hydrostatic strength and impact strength of the polypropylene pipe. The low-melt-index polypropylene is used as a carrier, and the low-melt-index polypropylene main material is used for pre-dispersing the composite auxiliary agent master batch, so that the composite auxiliary agent master batch has a melting state fluidity which is closer to that of the low-melt-index polypropylene main material, and no crystal phase separation occurs in the nucleating agent induced nucleation process.
Description
Technical Field
The invention relates to a composite auxiliary agent master batch special for polypropylene pipes and application thereof, relates to C08L, and in particular relates to the field of polymer compositions.
Background
The pipe is prepared from low-melt polypropylene, the prepared pipe has higher impact performance and hydrostatic strength, but the low-melt polypropylene has poor fluidity in a molten state due to poor fluidity in the processing process, and is easy to generate crystalline phase separation and change in a microscopic state in the nucleating agent induced nucleation process, so that the impact resistance of the polypropylene pipe is damaged. And polypropylene with low melt index is not easy to extrude in the process of processing and preparing the pipe, the surface effect of the formed melt is poor, and the melt is easy to accumulate in a machine and is subjected to oxidation at high temperature to cause yellowing, so that the appearance of the pipe is affected, and the development of a polypropylene processing aid which can promote the processing and promote the internal microstructure uniformity is important.
Chinese patent No. 202010781384.0 discloses a low-melt-index random copolymer polypropylene resin and a preparation method thereof, wherein propylene is subjected to bulk polymerization in a first loop reactor to form a homo-polypropylene matrix, and liquid-phase propylene and a small amount of ethylene are subjected to bulk random copolymerization in a second loop reactor to form an ethylene-propylene random copolymer, which has higher rigidity, heat distortion temperature and transparency, but poor shock resistance. The invention of China patent No. CN20231038335. X discloses a nucleating agent master batch, a preparation method thereof and application thereof in low-melt-index polypropylene materials, and high-melt-index PPH resin is used as carriers of two nucleating agents, so that the nucleating agents are dispersed more uniformly in a low-melt-index PPB resin system, and finally the rigidity of the PPB resin material is improved, but the preparation process is complicated because two nucleating agents are needed.
Disclosure of Invention
In order to optimize the impact resistance and hydrostatic strength of a pipe processed from low-melt polypropylene, the first aspect of the invention provides a special composite additive master batch for polypropylene pipes, which comprises the following preparation raw materials in percentage by weight: 10-20% of composite nucleating agent, 5-20% of antioxidant I, 1-5% of lubricant and the balance of polypropylene.
As a preferred embodiment, the polypropylene is a homo-polypropylene having a melt mass flow rate of 1-5g/10min at 230 ℃.
As a preferred embodiment, the composite nucleating agent comprises a modified reinforcing agent, a modified fluoropolymer, an organic carboxylate; the weight ratio of the modified reinforcing agent to the modified fluoropolymer to the organic carboxylate is (3-8): (1-5): (5-10).
As a preferred embodiment, the weight ratio of the modified reinforcing agent, modified fluoropolymer, and organic carboxylate is (4-7): (1-3): (7-9).
As a preferred embodiment, the modified reinforcing agent, modified fluoropolymer, organic carboxylate has a weight ratio of 5:2:8.
As a preferred embodiment, the modified reinforcing agent is selected from one or a combination of several of modified hydrotalcite, modified silica, modified carbon black, modified calcium carbonate and modified zinc oxide.
As a preferred embodiment, the modified reinforcing agent is modified hydrotalcite.
As a preferred embodiment, the modified reinforcing agent is a siloxane modified reinforcing agent, and the siloxane modified reinforcing agent is one or a combination of several of 3-aminopropyl triethoxysilane modified reinforcing agent, 3- (2-amino ethylamino) propyl trimethoxysilane modified reinforcing agent, octyl trimethoxysilane modified reinforcing agent and phenyl triethoxysilane modified reinforcing agent.
As a preferred embodiment, the modifying and reinforcing agent is 3-aminopropyl triethoxysilane modified hydrotalcite.
As a preferred embodiment, the preparation method of the 3-aminopropyl triethoxysilane modified hydrotalcite comprises the following steps:
S1, taking 80-90g of crushed hydrotalcite, taking methanol as a solvent, heating and refluxing at the temperature of 80-90 ℃, stirring at a high speed of 1200-1600r/min to form a suspension, and slowly adding 100-150mL of 3-aminopropyl triethoxysilane;
S2, continuously preserving heat, stirring and refluxing for 4-8 hours, filtering, drying and crushing for standby.
As a preferred embodiment, the preparation method of the 3-aminopropyl triethoxysilane modified hydrotalcite comprises the following steps:
S1, taking 82.5g of crushed hydrotalcite, taking methanol as a solvent, heating and refluxing at the temperature of 85 ℃, stirring at a high speed of 1500r/min to form a suspension, and slowly adding 120mL of 3-aminopropyl triethoxysilane;
S2, continuously preserving heat, stirring and refluxing for 5 hours, filtering, drying and crushing for later use.
As a preferred embodiment, the particle size D90 of the hydrotalcite after pulverization is less than 10 μm.
The hydrotalcite in the composite additive master batch for polypropylene is modified hydrotalcite, and simultaneously acts together with modified fluorine polymer, so that the fluidity of the low-melt-index polypropylene material when the low-melt-index polypropylene material is applied to pipes is improved, the structural uniformity of polypropylene is optimized, and the hydrostatic strength and impact strength of the polypropylene pipes are improved. The applicant finds that the modified hydrotalcite with scientific proportion is added into the pipe prepared from the low-melt polypropylene in the experimental process, the modified fluoropolymer and the organic carboxylate can optimize the structural uniformity of the polypropylene material, and in the nucleating agent induced nucleation process, the crystal phase separation cannot occur, and the possible reasons are hypothesized as follows: the hydrotalcite has high rigidity, spontaneous agglomeration can occur if no modification is performed, incompatible phases are formed with organic carboxylate, heterogeneous nucleation occurs, and the structural uniformity of polypropylene is destroyed. 3-aminopropyl triethoxy silane is modified on hydrotalcite by taking methanol as a solvent, an ethoxy structure of the silane is replaced by hydroxy in the methanol, intermolecular dehydration is carried out on hydroxy in the molecule, a reticular cross-linking structure of silanol is formed to wrap the hydrotalcite inside, the hydrotalcite outside is a low-polarity hydroxy chain and a derivative thereof, the compatibility with polypropylene is good, and heterogeneous nucleation caused by the introduction of hydrotalcite is avoided.
As a preferred embodiment, the modified fluoropolymer is selected from one or a combination of several of modified polytetrafluoroethylene, modified polyvinylidene fluoride, modified polyvinyl fluoride, modified polychlorotrifluoroethylene, and modified ethylene-tetrafluoroethylene copolymer.
As a preferred embodiment, the modified fluoropolymer is a modified polyvinylidene fluoride.
As a preferred embodiment, the modified fluoropolymer is selected from one or a combination of several of vinyltriethoxysilane modified fluoropolymer, vinyldiethylmethylsilane modified fluoropolymer, vinyltrimethoxysilane modified fluoropolymer, vinyltris (2-methoxyethoxy) silane modified fluoropolymer.
As a preferred embodiment, the modified polyvinylidene fluoride is vinyldiethylmethylsilane modified polyvinylidene fluoride.
As a preferred embodiment, the preparation method of the vinyldiethylmethylsilane modified polyvinylidene fluoride comprises the following steps:
M1, 50-60g of polyvinylidene fluoride is taken and poured into a stainless steel reactor, the materials are heated to be in a sticky state, and 14.5mL of vinyldiethyl methylsilane is slowly added;
and (3) preserving the temperature of M2, slowly stirring for 1-3h, cooling, introducing liquid nitrogen, crushing for multiple times, and controlling the particle size of the product.
As a preferred embodiment, the product particle size is D90 < 10. Mu.m.
As a preferred embodiment, the organic carboxylate is selected from one or a combination of several of sodium benzoate, aluminum benzoate, monohydroxy bis-p-tert-butyl aluminum benzoate, bicyclo [2, 1] heptane dicarboxylate.
Meanwhile, the applicant finds that the low-temperature flow rate of the polypropylene with low melt index is low, the processing performance in an extruder is poor, the extrusion molding is difficult, the extrusion of the polypropylene can be improved by introducing the fluoropolymer, but the effect is not obvious, the processing performance of the polypropylene can be greatly improved by modifying the fluoropolymer by vinyl diethoxymethylsilane, and the possible reasons are hypothesized to be: the hydroxyl-terminated groups of the polyvinylidene fluoride can be chemically bonded with the vinyl diethoxymethylsilane to play a traction role, so that the migration resistance of the polyvinylidene fluoride in the polypropylene is reduced under the action of silane groups, the outward migration of the polyvinylidene fluoride can be promoted, the external lubrication effect between a polypropylene melt and an extruder is increased, the adhesion of the polypropylene in the extruder is reduced, and the processability is improved.
As a preferred embodiment, the antioxidant I comprises antioxidant 1010 and antioxidant 168.
As a preferred embodiment, the weight ratio of the antioxidant 1010 to the antioxidant 168 is 1: (1-3), it is further preferable that the weight ratio of the antioxidant 1010 to the antioxidant 168 is 1:1.
As a preferred embodiment, the lubricant is calcium stearate.
The second aspect of the invention provides application of a special composite additive master batch for a polypropylene pipe, which is applied to the polypropylene pipe, wherein the polypropylene pipe comprises the following preparation raw materials in percentage by weight: 1-5% of composite auxiliary agent master batch, 1-10% of antioxidant II, 1-5% of light stabilizer and the balance of polypropylene main material.
As a preferred embodiment, the polypropylene main material has a melt mass flow rate of < 0.5g/10min at 230 ℃.
As a preferred embodiment, the antioxidant ii is antioxidant 330. The light stabilizer is light stabilizer 788.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the composite additive master batch special for the polypropylene pipe, the modified hydrotalcite and the modified fluoropolymer are adopted to act together, so that the fluidity of the low-melt-index polypropylene material when the low-melt-index polypropylene material is applied to the pipe is improved, the structural uniformity of polypropylene is optimized, and the hydrostatic strength and the impact resistance of the polypropylene pipe are improved.
(2) The special composite additive master batch for the polypropylene pipe adopts the vinyl silane modified fluoropolymer, so that the extrusion processing performance of the polypropylene pipe with low melt index can be improved, the adhesion of polypropylene in an extruder is reduced, and the processing performance is improved.
(3) The composite auxiliary master batch special for the polypropylene pipe uses the low-melt-index homogeneously nucleated polypropylene as the carrier, and the low-melt-index polypropylene main material is pre-dispersed to the composite auxiliary master batch, so that the composite auxiliary master batch has the fluidity in a melting state which is closer to that of the low-melt-index polypropylene main material, and the crystalline phase separation can not occur in the nucleating agent induced nucleation process.
Detailed Description
Example 1
The composite auxiliary agent master batch special for the polypropylene pipe comprises the following preparation raw materials in percentage by weight: 12% of composite nucleating agent, 10% of antioxidant I, 4% of lubricant and the balance of polypropylene.
The polypropylene is homopolymerized polypropylene, and the melt mass flow rate of the homopolymerized polypropylene at 230 ℃ is 3g/10min, and the brand is T03.
The composite nucleating agent is a modified reinforcing agent, a modified fluoropolymer and organic carboxylate in a weight ratio of 5:2:8.
The modified reinforcing agent is 3-aminopropyl triethoxysilane modified hydrotalcite, and the preparation method comprises the following steps: s1, taking 82.5g of crushed hydrotalcite, taking methanol as a solvent, heating and refluxing at the temperature of 85 ℃, stirring at a high speed of 1500r/min to form a suspension, and slowly adding 120mL of 3-aminopropyl triethoxysilane;
S2, continuously preserving heat, stirring and refluxing for 5 hours, filtering, drying and crushing for later use.
The particle size D90 of the crushed hydrotalcite is less than 10 mu m, and the hydrotalcite is purchased from Tay Bohai ocean chemical technology Co., ltd, and the model is HTB hydrotalcite.
The modified fluoropolymer is vinyl diethyl methylsilane modified polyvinylidene fluoride, and the preparation method comprises the following steps:
M1, 50g of polyvinylidene fluoride is taken and poured into a stainless steel reactor, the materials are heated to be in a bonding state, and 14.5mL of vinyldiethyl methylsilane is slowly added;
And (3) preserving the temperature of M2, slowly stirring for 2 hours, cooling, introducing liquid nitrogen, crushing for multiple times, and controlling the particle size D90 of the product to be less than 10 mu M.
The organic carboxylate is sodium benzoate.
The antioxidant I is an antioxidant 1010 and an antioxidant 168, and the weight ratio is 1:1.
The lubricant is calcium stearate.
The preparation method of the special composite auxiliary agent master batch for the polypropylene pipe comprises the following steps: mixing the composite nucleating agent, the antioxidant I, the lubricant and the polypropylene in a high-speed mixer in proportion, and then adding the mixture into a double-screw extruder for extrusion granulation to obtain the composite auxiliary agent master batch. The temperature of the twin-screw extruder was 220 ℃.
The application of the composite auxiliary agent master batch special for the polypropylene pipe is applied to the polypropylene pipe, and the preparation raw materials comprise the following components in percentage by weight: 3% of composite additive master batch, 5% of antioxidant II, 2% of light stabilizer and the balance of polypropylene main material.
The polypropylene main material has a melt mass flow rate of 0.3g/10min at 230 ℃ and is purchased from Beijing Yanshan with the brand of B8101.
The antioxidant II is an antioxidant 330. The light stabilizer is light stabilizer 788.
The preparation method of the polypropylene pipe comprises the following steps: and mixing the polypropylene main material with the composite auxiliary agent master batch, adding an antioxidant II and a light stabilizer, mixing in a high-speed mixer, extruding in an extruder, preparing a sample, and testing.
The extruder temperature was 280 ℃.
Example 2
The composite auxiliary agent master batch special for the polypropylene pipe comprises the following preparation raw materials in percentage by weight: 10% of composite nucleating agent, 8% of antioxidant I, 1% of lubricant and the balance of polypropylene.
The polypropylene is homopolymerized polypropylene, and the melt mass flow rate of the homopolymerized polypropylene at 230 ℃ is 3g/10min, and the brand is T03.
The composite nucleating agent is a modified reinforcing agent, a modified fluoropolymer and organic carboxylate in a weight ratio of 5:2:8.
The modified reinforcing agent is 3- (2-amino ethyl amino) propyl trimethoxy silane modified hydrotalcite, and the preparation method comprises the following steps:
s1, taking 82.5g of crushed hydrotalcite, taking methanol as a solvent, heating and refluxing at the temperature of 85 ℃, stirring at a high speed of 1500r/min to form a suspension, and slowly adding 120mL of 3- (2-amino-ethylamino) propyl trimethoxy silane;
S2, continuously preserving heat, stirring and refluxing for 5 hours, filtering, drying and crushing for later use.
The particle size D90 of the crushed hydrotalcite is less than 10 mu m, and the hydrotalcite is purchased from Tay Bohai ocean chemical technology Co., ltd, and the model is HTB hydrotalcite.
The modified fluoropolymer is vinyltriethoxysilane modified polyvinylidene fluoride, and the preparation method comprises the following steps:
m1, 50g of polyvinylidene fluoride is taken and poured into a stainless steel reactor, the materials are heated to be in a bonding state, and 14.5mL of vinyltriethoxysilane is slowly added;
And (3) preserving the temperature of M2, slowly stirring for 2 hours, cooling, introducing liquid nitrogen, crushing for multiple times, and controlling the particle size D90 of the product to be less than 10 mu M.
The organic carboxylate is aluminum benzoate.
The antioxidant I is an antioxidant 1010 and an antioxidant 168, and the weight ratio is 1:1.
The lubricant is calcium stearate.
The preparation method of the special composite auxiliary agent master batch for the polypropylene pipe comprises the following steps: mixing the composite nucleating agent, the antioxidant I, the lubricant and the polypropylene in a high-speed mixer in proportion, and then adding the mixture into a double-screw extruder for extrusion granulation to obtain the composite auxiliary agent master batch. The temperature of the twin-screw extruder was 220 ℃.
The application of the composite auxiliary agent master batch special for the polypropylene pipe is applied to the polypropylene pipe, and the preparation raw materials comprise the following components in percentage by weight: 2% of composite auxiliary agent master batch, 3% of antioxidant II, 4% of light stabilizer and the balance of polypropylene main material.
The polypropylene main material has a melt mass flow rate of 0.3g/10min at 230 ℃ and is purchased from Beijing Yanshan with the brand of B8101.
The antioxidant II is an antioxidant 330. The light stabilizer is light stabilizer 788.
The preparation method of the polypropylene pipe comprises the following steps: and mixing the polypropylene main material with the composite auxiliary agent master batch, adding an antioxidant II and a light stabilizer, mixing in a high-speed mixer, extruding in an extruder, preparing a sample, and testing.
The extruder temperature was 280 ℃.
Example 3
The composite auxiliary agent master batch special for the polypropylene pipe comprises the following preparation raw materials in percentage by weight: 20% of composite nucleating agent, 16% of antioxidant I, 5% of lubricant and the balance of polypropylene.
The polypropylene is homopolymerized polypropylene, and the melt mass flow rate of the homopolymerized polypropylene at 230 ℃ is 3g/10min, and the brand is T03.
The composite nucleating agent is a modified reinforcing agent, a modified fluoropolymer and organic carboxylate in a weight ratio of 5:2:8.
The modified reinforcing agent is octyl trimethoxy silane modified hydrotalcite, and the preparation method comprises the following steps:
S1, taking 82.5g of crushed hydrotalcite, taking methanol as a solvent, heating and refluxing at the temperature of 85 ℃, stirring at a high speed of 1500r/min to form a suspension, and slowly adding 120mL of octyl trimethoxy silane;
S2, continuously preserving heat, stirring and refluxing for 5 hours, filtering, drying and crushing for later use.
The particle size D90 of the crushed hydrotalcite is less than 10 mu m, and the hydrotalcite is purchased from Tay Bohai ocean chemical technology Co., ltd, and the model is HTB hydrotalcite.
The modified fluoropolymer is vinyl trimethoxy silane modified polyvinylidene fluoride, and the preparation method comprises the following steps:
M1, 50g of polyvinylidene fluoride is taken and poured into a stainless steel reactor, the materials are heated to be in a bonding state, and 14.5mL of vinyltrimethoxysilane is slowly added;
And (3) preserving the temperature of M2, slowly stirring for 2 hours, cooling, introducing liquid nitrogen, crushing for multiple times, and controlling the particle size D90 of the product to be less than 10 mu M.
The organic carboxylate is monohydroxy aluminum bis-p-tert-butylbenzoate.
The antioxidant I is an antioxidant 1010 and an antioxidant 168, and the weight ratio is 1:1.
The lubricant is calcium stearate.
The preparation method of the special composite auxiliary agent master batch for the polypropylene pipe comprises the following steps: mixing the composite nucleating agent, the antioxidant I, the lubricant and the polypropylene in a high-speed mixer in proportion, and then adding the mixture into a double-screw extruder for extrusion granulation to obtain the composite auxiliary agent master batch. The temperature of the twin-screw extruder was 220 ℃.
The application of the composite auxiliary agent master batch special for the polypropylene pipe is applied to the polypropylene pipe, and the preparation raw materials comprise the following components in percentage by weight: 5% of composite additive master batch, 8% of antioxidant II, 1% of light stabilizer and the balance of polypropylene main material.
The polypropylene main material has a melt mass flow rate of 0.3g/10min at 230 ℃ and is purchased from Beijing Yanshan with the brand of B8101.
The antioxidant II is an antioxidant 330. The light stabilizer is light stabilizer 788.
The preparation method of the polypropylene pipe comprises the following steps: and mixing the polypropylene main material with the composite auxiliary agent master batch, adding an antioxidant II and a light stabilizer, mixing in a high-speed mixer, extruding in an extruder, preparing a sample, and testing.
The extruder temperature was 280 ℃.
Comparative example 1
The specific preparation raw materials and the addition amount of the polypropylene pipe are the same as those in example 1, and the difference is that: the preparation method comprises the steps of directly adding the preparation raw materials of the composite auxiliary agent master batch into the polypropylene main material for mixing without pre-processing, then adding an antioxidant II and a light stabilizer, mixing in a high-speed mixer, extruding in an extruder, preparing samples, and testing.
Comparative example 2
The specific implementation mode of the composite auxiliary agent master batch special for the polypropylene pipe is the same as example 1, and the difference is that the composite nucleating agent is a combination of hydrotalcite, modified fluoropolymer and organic carboxylate, and the weight ratio is 5:2:8.
Comparative example 3
The specific implementation mode of the composite additive master batch special for the polypropylene pipe is the same as that of the example 1, and the specific implementation mode is different in that the particle size of hydrotalcite is 100 mu m, and the hydrotalcite is purchased from Tay Bohai ocean chemical engineering Co., ltd, and the model is HTB hydrotalcite.
Comparative example 4
The specific implementation mode of the composite auxiliary agent master batch special for the polypropylene pipe is the same as example 1, and the difference is that the modified fluoropolymer is 3-aminopropyl triethoxysilane modified polyvinylidene fluoride.
Comparative example 5
The specific implementation mode of the composite auxiliary agent master batch special for the polypropylene pipe is the same as that of the example 1, and the difference is that the modified reinforcing agent is vinyl diethyl methylsilane modified hydrotalcite.
Performance testing
1. Flexural modulus: flexural modulus was measured for examples and comparative examples with reference to GB/T9341-2008 standard.
2. Impact strength of simple beam: the examples and comparative examples were tested for impact strength at-20℃with reference to GB/T1043.1-2008 standard.
3. Yellow index: the yellowness index of examples and comparative examples was tested with reference to the GB 2409-80 standard.
4. Hydrostatic testing: the examples and comparative examples were tested with reference to GB/T18742.2-2017 standards for hydrostatic strength at 95℃C, 165h,4MPa and 95℃C, 1000h,3.5 MPa.
5. Gloss test: ISO 2813-method for measuring gloss of paint film, which selects 60 degree reflected light angle to evaluate the ability of reflecting light on the surface of the material.
The test results are shown in Table 1.
TABLE 1
Claims (10)
1. The special composite auxiliary agent master batch for the polypropylene pipe is characterized by comprising the following preparation raw materials in percentage by weight: 10-20% of composite nucleating agent, 5-20% of antioxidant I, 1-5% of lubricant and the balance of polypropylene.
2. The special composite additive master batch for polypropylene pipes according to claim 1, wherein the polypropylene is homo-polypropylene, and the melt mass flow rate of the homo-polypropylene at 230 ℃ is 1-5g/10min.
3. The special composite auxiliary agent master batch for the polypropylene pipe according to claim 1, wherein the composite nucleating agent comprises a modified reinforcing agent, a modified fluoropolymer and an organic carboxylate; the weight ratio of the modified reinforcing agent to the modified fluoropolymer to the organic carboxylate is (3-8): (1-5): (5-10).
4. The special composite auxiliary agent master batch for polypropylene pipes according to claim 3, wherein the weight ratio of the modified reinforcing agent, the modified fluoropolymer and the organic carboxylate is (4-7): (1-3): (7-9).
5. The composite additive master batch special for polypropylene pipes according to claim 3, wherein the modified reinforcing agent is one or a combination of a plurality of modified hydrotalcite, modified silicon dioxide, modified carbon black, modified calcium carbonate and modified zinc oxide.
6. The special composite additive master batch for polypropylene pipes according to claim 5, wherein the modified reinforcing agent is a siloxane modified reinforcing agent, and the siloxane modified reinforcing agent is one or a combination of more of a 3-aminopropyl triethoxysilane modified reinforcing agent, a 3- (2-amino ethylamino) propyl trimethoxysilane modified reinforcing agent, an octyl trimethoxysilane modified reinforcing agent and a phenyl triethoxysilane modified reinforcing agent.
7. The special composite additive master batch for polypropylene pipes according to claim 6, wherein the modified reinforcing agent is 3-aminopropyl triethoxysilane modified hydrotalcite, and the preparation method of the 3-aminopropyl triethoxysilane modified hydrotalcite comprises the following steps:
S1, taking 80-90g of crushed hydrotalcite, taking methanol as a solvent, heating and refluxing at the temperature of 80-90 ℃, stirring at a high speed of 1200-1600r/min to form a suspension, and slowly adding 100-150mL of 3-aminopropyl triethoxysilane;
S2, continuously preserving heat, stirring and refluxing for 4-8 hours, filtering, drying and crushing for standby.
8. The polypropylene pipe special composite additive master batch according to claim 3, wherein the modified fluoropolymer is selected from one or a combination of more of modified polytetrafluoroethylene, modified polyvinylidene fluoride, modified polyvinyl fluoride, modified polychlorotrifluoroethylene and modified ethylene-tetrafluoroethylene copolymer.
9. The application of the special composite auxiliary master batch for the polypropylene pipe according to any one of claims 1 to 8, which is characterized in that the special composite auxiliary master batch for the polypropylene pipe is applied to the polypropylene pipe, and the preparation raw materials of the polypropylene pipe comprise the following components in percentage by weight: 1-5% of composite auxiliary agent master batch, 1-10% of antioxidant II, 1-5% of light stabilizer and the balance of polypropylene main material.
10. The application of the special composite additive master batch for the polypropylene pipe according to claim 9, wherein the melt mass flow rate of the polypropylene main material at 230 ℃ is less than 0.5g/10min; the antioxidant I comprises an antioxidant 1010 and an antioxidant 168; the lubricant is calcium stearate; the antioxidant II is an antioxidant 330; the light stabilizer is light stabilizer 788.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410135250.XA CN117887170A (en) | 2024-01-31 | 2024-01-31 | Composite auxiliary agent master batch special for polypropylene pipe and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410135250.XA CN117887170A (en) | 2024-01-31 | 2024-01-31 | Composite auxiliary agent master batch special for polypropylene pipe and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117887170A true CN117887170A (en) | 2024-04-16 |
Family
ID=90650523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410135250.XA Pending CN117887170A (en) | 2024-01-31 | 2024-01-31 | Composite auxiliary agent master batch special for polypropylene pipe and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117887170A (en) |
-
2024
- 2024-01-31 CN CN202410135250.XA patent/CN117887170A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114525017B (en) | Semi-aromatic carbon dioxide based copolymer high-toughness composition and preparation method thereof | |
| CN102643480B (en) | Anti-static alloy composite material and preparation method thereof | |
| CN102218879A (en) | Waste polypropylene-modified foaming plate and manufacturing method thereof | |
| CN101065425A (en) | Foamable composition | |
| CN113388194B (en) | Glass fiber reinforced polypropylene composition and preparation method and application thereof | |
| CN1919915B (en) | Modified polypropylene material for refrigerator and manufacture method thereof | |
| CN113736177B (en) | Weather-resistant master batch UV-7308PP5 and preparation method and application thereof | |
| CN106317571A (en) | High strength ultraviolet resistant PE/ PET composite material and preparation method thereof | |
| CN113930068A (en) | Preparation method of hollow glass bead master batch | |
| CN103360732A (en) | Alloy for recovering polyethylene glycol terephthalate/acrylonitrile-butadiene-styrene copolymer and preparation method thereof | |
| CN108384208B (en) | PET-based wood-plastic composite material and preparation method thereof | |
| CN112028929A (en) | Preparation method and application of polyhedral oligomeric silsesquioxane-loaded substituted aryl heterocyclic phosphate or salt nucleating agent | |
| CN111718500B (en) | Filling master batch, preparation method and application thereof, and modified plastic | |
| CN117887170A (en) | Composite auxiliary agent master batch special for polypropylene pipe and application thereof | |
| CN113603994A (en) | High-thermal-oxygen-stability high-heat-resistance spraying-free PMMA/ASA alloy resin composition and preparation method thereof | |
| CN109486156B (en) | Flame-retardant extrusion-grade PC/ABS composite material | |
| CN107955270B (en) | Polypropylene nano composite material and preparation method thereof | |
| CN109161177B (en) | Polymethyl ethylene carbonate based high-barrier material and preparation method thereof | |
| CN104629294A (en) | PC / ABS modified alloy with excellent mechanical properties | |
| CN106832893A (en) | A kind of isomerism of crosslinking agents of POSS containing L reclaims nylon and preparation method thereof | |
| CN103756110B (en) | The production technology that a kind of drip irrigation zone thermostability improves | |
| CN112029296A (en) | Organic carrier-free polysiloxane particles and preparation method thereof | |
| CN113087987A (en) | Modified rice hull powder/polyethylene wood-plastic composite material and preparation method thereof | |
| CN116199975B (en) | Polypropylene modified material and preparation method and application thereof | |
| CN110467790B (en) | Long glass fiber reinforced polypropylene composite material for foaming and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination |