CN117624789B - Modified polypropylene composite pipe and preparation process thereof - Google Patents
Modified polypropylene composite pipe and preparation process thereof Download PDFInfo
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- CN117624789B CN117624789B CN202311631816.XA CN202311631816A CN117624789B CN 117624789 B CN117624789 B CN 117624789B CN 202311631816 A CN202311631816 A CN 202311631816A CN 117624789 B CN117624789 B CN 117624789B
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- -1 polypropylene Polymers 0.000 title claims abstract description 75
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 70
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 70
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000003063 flame retardant Substances 0.000 claims abstract description 46
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims description 26
- 238000004132 cross linking Methods 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 20
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 15
- 229920005604 random copolymer Polymers 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000003963 antioxidant agent Substances 0.000 claims description 14
- 230000003078 antioxidant effect Effects 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- 230000006835 compression Effects 0.000 claims description 8
- 238000007906 compression Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 8
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims description 8
- 238000007493 shaping process Methods 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000005502 peroxidation Methods 0.000 claims description 7
- KMRIWYPVRWEWRG-UHFFFAOYSA-N 2-(6-oxobenzo[c][2,1]benzoxaphosphinin-6-yl)benzene-1,4-diol Chemical compound OC1=CC=C(O)C(P2(=O)C3=CC=CC=C3C3=CC=CC=C3O2)=C1 KMRIWYPVRWEWRG-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 229940057995 liquid paraffin Drugs 0.000 claims description 6
- 239000000314 lubricant Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- FYGUSUBEMUKACF-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-5-carboxylic acid Chemical compound C1C2C(C(=O)O)CC1C=C2 FYGUSUBEMUKACF-UHFFFAOYSA-N 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 230000001737 promoting effect Effects 0.000 claims description 4
- 239000011343 solid material Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 3
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000005764 inhibitory process Effects 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- GWHOGODUVLQCEB-UHFFFAOYSA-N pyridine-2,6-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=N1 GWHOGODUVLQCEB-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000001993 wax Substances 0.000 claims description 3
- 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 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 7
- 230000007774 longterm Effects 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001263 acyl chlorides Chemical group 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- LJUXFZKADKLISH-UHFFFAOYSA-N benzo[f]phosphinoline Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=P1 LJUXFZKADKLISH-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of high polymer materials and discloses a modified polypropylene composite pipe and a preparation process thereof. The high-molecular halogen-free flame retardant component is used for filling, and the characteristic of the intumescent flame retardant can be utilized, so that the prepared polypropylene pipe has good fireproof flame retardant property, and the high-molecular halogen-free flame retardant is not easy to volatilize and migrate, so that the long-term flame retardant effect of the polypropylene composite pipe is ensured.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a modified polypropylene composite pipe and a preparation process thereof.
Background
Polypropylene (PP) is a thermoplastic resin for short, and is widely used for manufacturing various products, and has the characteristics of light weight, low cost, small density, good stability, corrosion resistance and the like, so that the polypropylene is widely applied to the fields of cable jackets, building pipelines and the like. At present, the frequency of fire occurrence of urban high-rise buildings is higher and higher, so that the fireproof and flame-retardant performance of building materials is subjected to more and more severe requirements, the limiting oxygen index of polypropylene is 18%, the polypropylene belongs to inflammable materials, and the polypropylene can generate molten dripping during combustion to cause further spread of fire, so that the polypropylene has potential safety hazards to life and property safety of residents. In addition, polypropylene is relatively poor in high temperature resistance, and the long-term use temperature of the polypropylene is not higher than 80 ℃, otherwise the ageing and damage of the pipeline are accelerated, and the polypropylene is gradually limited in application in the field of building pipelines.
The flame retardant property of polypropylene can be improved to a certain extent by adding the additive with flame retardant effect into polypropylene pipe, the invention patent publication No. CN114410008A discloses a non-halogen flame retardant polypropylene pipe and a preparation method thereof, the flame retardant property of polypropylene is improved by using an aluminophosphate flame retardant as the non-halogen flame retardant, but the flame retardant effect of inorganic filler is general, and from the aspects of a formula and a test result, the additive amount is large, and the limiting oxygen index of the finally prepared polypropylene pipe is only 23 percent, and still belongs to inflammable materials, so that the actual effect is not obvious.
Based on the above, the invention provides the modified polypropylene composite pipe, which has good flame retardant property and high temperature resistance, and can be directly applied to the field of building pipelines.
Disclosure of Invention
The invention aims to provide a modified polypropylene composite pipe and a preparation process thereof, which solve the problems of poor thermal stability and poor flame retardant property of the polypropylene pipe.
The aim of the invention can be achieved by the following technical scheme:
a preparation process of a modified polypropylene composite pipe comprises the following steps:
first step, mixing materials
Sequentially adding the random copolymer polypropylene, the crosslinking component, the high-molecular halogen-free flame retardant component, the peroxidation initiator, the filler, the compatilizer, the lubricant and the antioxidant auxiliary agent into a high-speed mixer, mixing for 20-30min at a stirring rate of 400-500r/min, and recording the mixture as a premix;
second step, extrusion
Adding the premix into an extruder, setting the temperature of a feeding section of the extruder to 170+/-5 ℃, setting the temperature of a compression section to 190+/-5 ℃, setting the temperature of a plasticizing section to 200+/-5 ℃, setting the temperature of a homogenizing section to 210+/-5 ℃, setting the temperature of a die orifice to 200+/-5 ℃, controlling the rotating speed of a screw to 80-100r/min, and cooling and shaping after melt extrusion to obtain the polypropylene composite pipe.
Specifically, the structure of the crosslinking component contains two equivalent norbornene structures, and the norbornene structures can be subjected to high-temperature melt polymerization with the random copolymer polypropylene under the action of a peroxidation initiator, so that the random copolymer polypropylene has a three-dimensional crosslinking structure by utilizing the crosslinking effect of the crosslinking component, and the toughness of the polypropylene can be improved.
Further preferably, the polypropylene composite pipe is prepared from the following raw materials in parts by weight: 75-85 parts of random copolymer polypropylene, 3-6 parts of crosslinking component, 3-5 parts of high polymer halogen-free flame retardant component, 0.5-1 part of peroxidation initiator, 10-15 parts of filler, 10-20 parts of compatilizer, 1-2 parts of lubricant and 0.5-1.5 parts of antioxidant auxiliary agent.
Further preferably, the preparation method of the crosslinking component is as follows:
mixing the dihydroxy-terminated polyphenyl ether and chloroform, adding a mixed catalyst into the formed liquid, stirring for 1-2 hours at room temperature after adding, introducing nitrogen for oxygen removal, adding 5-norbornene-2-carboxylic acid into the mixed liquid, continuously stirring for 4-6 hours at room temperature, pouring into a mixed solution of isopropanol and anhydrous diethyl ether with the volume ratio of 3:7 for precipitation, taking the precipitate, washing for removing impurities, and drying in a vacuum drying oven at 60 ℃ for 8-12 hours to obtain the crosslinking component.
Further preferably, the molecular weight of the dihydroxy terminated polyphenylene ether is 5000.
Further preferably, the mixed catalyst comprises N-hydroxysuccinimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride in a mass ratio of 0.2-0.3:1.
Specifically, the double-hydroxyl end-capped polyphenyl ether contains an end-activated hydroxyl group, can interact with carboxyl in a 5-norbornene-2-carboxylic acid structure after being activated by a catalyst, and is condensed, so that the double-end-capped polyphenyl ether is formed, and the norbornene contains unsaturated alkenyl, so that the double-end-capped polyphenyl ether can be crosslinked and polymerized with random copolymer polypropylene, namely a crosslinking component.
Further preferably, the preparation method of the polymer halogen-free flame retardant component is as follows:
mixing 2, 6-pyridine diformyl chloride and tetrahydrofuran, placing in a polymerization kettle, stirring to form a uniform solution, introducing nitrogen, exhausting air in the polymerization kettle, adding 10- (2, 5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide into the polymerization kettle under the stirring condition, dripping a promoting auxiliary agent, continuously stirring and mixing for 12-18H at room temperature, adding phenol for polymerization inhibition, stirring for 1-2H, evaporating to remove a solvent, taking a solid material, washing to remove impurities, and drying to obtain the high-molecular halogen-free flame-retardant component.
Further preferably, the mass ratio of the 2, 6-pyridine dicarboxylic acid dichloride to the 10- (2, 5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide is 1:1.5-1.55.
Further preferably, the promoter is at least one of triethylamine or pyridine.
Specifically, the 2, 6-pyridine dicarboxylic acid dichloride contains two equivalents of acyl chloride substituent groups, and can be subjected to continuous esterification reaction with two equivalents of active hydroxyl substituent groups in 10- (2, 5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide under the action of a promoting auxiliary agent, so that an interconnected polyester type polymer, namely a polymer halogen-free flame retardant component, is formed, pyridine in the structure can be used as a nitrogen source and a carbon source, and a phosphaphenanthrene structure can be used as an acid source, so that the flame retardant has the effect of an intumescent flame retardant.
Further preferably, the peroxidation initiator is at least one of benzoyl peroxide or dicumyl peroxide; the filler is a compound of talcum powder and calcium carbonate, and the mass ratio is 1:1; the compatilizer is at least one of maleic anhydride grafted polyethylene or maleic anhydride grafted polypropylene; the lubricant is at least one of calcium stearate, liquid paraffin or polyethylene wax; the antioxidant auxiliary agent is at least one of antioxidant BHT, antioxidant 168 or antioxidant 1076.
The modified polypropylene composite pipe is prepared by adopting the preparation process.
The invention has the beneficial effects that:
according to the invention, the cross-linking component is prepared to cross-link the random copolymer polypropylene, so that the random copolymer polypropylene has a three-dimensional network structure, the mechanical property of the polypropylene composite pipe can be improved to a certain extent, and the cross-linking component contains a large number of rigid benzene rings and norbornene rigid structures, so that the rigidity of the three-dimensional network can be effectively improved, and the thermal stability of the polypropylene composite pipe can be effectively improved.
The polymer halogen-free flame retardant component prepared by the invention has the characteristic of an intumescent flame retardant, so that the flame retardant property of the polypropylene composite pipe can be greatly enhanced by less additive amount, and the limit oxygen index of the polypropylene composite pipe prepared by adding the polymer halogen-free flame retardant can reach 33.8% at most, and the combustion grade is V-0 grade, thus the polypropylene composite pipe belongs to flame retardant materials. In addition, the high-molecular halogen-free flame retardant is not easy to volatilize and migrate, so that the long-term flame retardant effect of the polypropylene composite pipe can be ensured.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an infrared spectrum of a crosslinking component prepared in example 1 of the present invention;
FIG. 2 is an infrared spectrum of the polymer halogen-free flame retardant component prepared in example 2 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preparation of the crosslinking component
3.5g of dihydroxyl-terminated polyphenyl ether with molecular weight of 5000 is mixed with chloroform, 0.01g of N-hydroxysuccinimide and 0.05g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride are added into the formed liquid, after the addition, stirring is carried out for 2 hours at room temperature, nitrogen is introduced for oxygen removal, then 0.2g of 5-norbornene-2-carboxylic acid is added into the mixed liquid, stirring is carried out for 6 hours at room temperature continuously, the mixed liquid is poured into a mixed solution of isopropanol and anhydrous diethyl ether with volume ratio of 3:7 for precipitation, the precipitate is taken, and after washing and impurity removal, the precipitate is dried in a vacuum drying oven at 60 ℃ for 12 hours, thus obtaining the crosslinking component.
The prepared crosslinking component iS tested on a Nicolet iS50 type infrared spectrometer in a manner of tabletting potassium bromide, and the scanning range iS 4000-500 cm -1 The results are shown in FIG. 1, which shows 3007cm by analysis -1 The absorption peak is the absorption peak of the hydrocarbon stretching vibration on C=C in norbornene, 3055-3085 cm -1 The absorption peak is a hydrocarbon telescopic vibration absorption peak on benzene ring in polyphenyl ether, 1746cm -1 The absorption peak appearing at this point is a c=o stretching vibration characteristic absorption peak of the ester group.
Example 2
The preparation method of the polymer halogen-free flame retardant component is as follows:
mixing 1.5g of 2, 6-pyridine diformyl chloride and tetrahydrofuran, placing the mixture in a polymerization kettle, stirring the mixture until a uniform solution is formed, introducing nitrogen, exhausting air in the polymerization kettle, adding 2.3g of 10- (2, 5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide into the polymerization kettle under the stirring condition, dropwise adding triethylamine, continuously stirring and mixing the mixture at room temperature for 16 hours after the addition of triethylamine, adding phenol for polymerization inhibition, stirring the mixture for 2 hours, evaporating the solvent, taking solid materials, washing, removing impurities and drying the solid materials to obtain the high-molecular halogen-free flame retardant component.
FIG. 2 is an infrared spectrum of a polymer halogen-free flame retardant component, analyzed, 3035-3095 cm -1 The absorption peak at the position is attributed to the absorption peak of the hydrocarbon stretching vibration on the benzene ring, which is 1728cm -1 The absorption peak appearing at the position is attributed to the carbon-oxygen double bond absorption peak in the ester group, and the fact that the high polymer halogen-free flame retardant component is connected through the ester bond is proved to be 1496cm -1 The absorption peak appearing at the position is attributed to C=N telescopic vibration absorption peak in pyridine, 1288cm -1 The absorption peak appearing at this point is attributed to the p=o stretching vibration absorption peak.
Example 3
A preparation process of a modified polypropylene composite pipe comprises the following steps:
first step, mixing materials
75 parts of random copolymer polypropylene, 3 parts of the crosslinking component prepared in the embodiment 1 of the invention, 3 parts of the high-molecular halogen-free flame retardant component prepared in the embodiment 2 of the invention, 0.5 part of benzoyl peroxide, 5 parts of talcum powder, 5 parts of calcium carbonate, 10 parts of maleic anhydride grafted polypropylene, 1 part of calcium stearate and 0.5 part of antioxidant auxiliary agent BHT are sequentially added into a high-speed mixer, and mixed for 30 minutes at a stirring rate of 400r/min, and the obtained mixture is recorded as a premix;
second step, extrusion
Adding the premix into an extruder, setting the temperature of a feeding section of the extruder to 170 ℃, setting the temperature of a compression section to 190 ℃, setting the temperature of a plasticizing section to 200 ℃, setting the temperature of a homogenizing section to 210 ℃, setting the temperature of a die orifice to 200 ℃, controlling the rotating speed of a screw to 100r/min, melting, extruding, and cooling and shaping to obtain the polypropylene composite pipe.
Example 4
A preparation process of a modified polypropylene composite pipe comprises the following steps:
first step, mixing materials
80 parts of random copolymer polypropylene, 5 parts of the crosslinking component prepared in the embodiment 1 of the invention, 4 parts of the high-molecular halogen-free flame retardant component prepared in the embodiment 2 of the invention, 0.6 part of dicumyl peroxide, 6 parts of talcum powder, 6 parts of calcium carbonate, 12 parts of maleic anhydride grafted polypropylene, 2 parts of liquid paraffin and 1 part of antioxidant auxiliary 168 are sequentially added into a high-speed mixer, and after mixing for 30 minutes at a stirring rate of 500r/min, the obtained mixture is recorded as a premix;
second step, extrusion
Adding the premix into an extruder, setting the temperature of a feeding section of the extruder to 170 ℃, setting the temperature of a compression section to 190 ℃, setting the temperature of a plasticizing section to 200 ℃, setting the temperature of a homogenizing section to 210 ℃, setting the temperature of a die orifice to 200 ℃, controlling the rotating speed of a screw to 100r/min, melting, extruding, and cooling and shaping to obtain the polypropylene composite pipe.
Example 5
A preparation process of a modified polypropylene composite pipe comprises the following steps:
first step, mixing materials
85 parts of random copolymer polypropylene, 6 parts of the crosslinking component prepared in the embodiment 1 of the invention, 5 parts of the high-molecular halogen-free flame retardant component prepared in the embodiment 2 of the invention, 1 part of dicumyl peroxide, 7.5 parts of talcum powder, 7.5 parts of calcium carbonate, 20 parts of maleic anhydride grafted polypropylene, 2 parts of polyethylene wax and 1.5 parts of antioxidant auxiliary 1076 are sequentially added into a high-speed mixer, and mixed for 20 minutes at a stirring rate of 500r/min, and the obtained mixture is recorded as a premix;
second step, extrusion
Adding the premix into an extruder, setting the temperature of a feeding section of the extruder to 170 ℃, setting the temperature of a compression section to 190 ℃, setting the temperature of a plasticizing section to 200 ℃, setting the temperature of a homogenizing section to 210 ℃, setting the temperature of a die orifice to 200 ℃, controlling the rotating speed of a screw to 100r/min, melting, extruding, and cooling and shaping to obtain the polypropylene composite pipe.
Comparative example 1
A preparation process of a modified polypropylene composite pipe comprises the following steps:
first step, mixing materials
80 parts of random copolymer polypropylene, 4 parts of the high polymer halogen-free flame retardant component prepared in the embodiment 2 of the invention, 6 parts of talcum powder, 6 parts of calcium carbonate, 12 parts of maleic anhydride grafted polypropylene, 2 parts of liquid paraffin and 1 part of antioxidant auxiliary 168 are sequentially added into a high-speed mixer, and are mixed for 30 minutes at a stirring rate of 500r/min, and the obtained mixture is recorded as a premix;
second step, extrusion
Adding the premix into an extruder, setting the temperature of a feeding section of the extruder to 170 ℃, setting the temperature of a compression section to 190 ℃, setting the temperature of a plasticizing section to 200 ℃, setting the temperature of a homogenizing section to 210 ℃, setting the temperature of a die orifice to 200 ℃, controlling the rotating speed of a screw to 100r/min, melting, extruding, and cooling and shaping to obtain the polypropylene composite pipe.
Comparative example 2
A preparation process of a modified polypropylene composite pipe comprises the following steps:
first step, mixing materials
80 parts of random copolymer polypropylene, 5 parts of the crosslinking component prepared in the embodiment 1 of the invention, 0.6 part of dicumyl peroxide, 6 parts of talcum powder, 6 parts of calcium carbonate, 12 parts of maleic anhydride grafted polypropylene, 2 parts of liquid paraffin and 1 part of antioxidant auxiliary 168 are sequentially added into a high-speed mixer, and mixed for 30 minutes at a stirring rate of 500r/min, and the obtained mixture is recorded as a premix;
second step, extrusion
Adding the premix into an extruder, setting the temperature of a feeding section of the extruder to 170 ℃, setting the temperature of a compression section to 190 ℃, setting the temperature of a plasticizing section to 200 ℃, setting the temperature of a homogenizing section to 210 ℃, setting the temperature of a die orifice to 200 ℃, controlling the rotating speed of a screw to 100r/min, melting, extruding, and cooling and shaping to obtain the polypropylene composite pipe.
Comparative example 3
A preparation process of a modified polypropylene composite pipe comprises the following steps:
first step, mixing materials
Sequentially adding 80 parts of random copolymer polypropylene, 6 parts of talcum powder, 6 parts of calcium carbonate, 12 parts of maleic anhydride grafted polypropylene, 2 parts of liquid paraffin and 1 part of antioxidant auxiliary 168 into a high-speed mixer, mixing for 30min at a stirring rate of 500r/min, and marking the mixture as a premix;
second step, extrusion
Adding the premix into an extruder, setting the temperature of a feeding section of the extruder to 170 ℃, setting the temperature of a compression section to 190 ℃, setting the temperature of a plasticizing section to 200 ℃, setting the temperature of a homogenizing section to 210 ℃, setting the temperature of a die orifice to 200 ℃, controlling the rotating speed of a screw to 100r/min, melting, extruding, and cooling and shaping to obtain the polypropylene composite pipe.
The polypropylene composite tubing of the present invention of examples 3-5 and comparative examples 1-3 was made into test bars conforming to the respective tests, and the following performance tests were performed:
testing the tensile strength of the bars according to GB/T10401.1-2006; testing the Vicat softening temperature of the sample bar according to GB/T1633-2000; according to GB/T2406.2-2009, the limiting oxygen index of a spline is tested, the UL-94 grade of the spline is tested, the fireproof and flame-retardant properties of the spline are analyzed, and the test results are shown in the following table:
| tensile Strength/MPa | Vicat softening temperature/DEGC | Oxygen index/% | UL-94 rating | |
| Example 3 | 31.0 | 149 | 33..5 | V-0 |
| Example 4 | 31.4 | 151 | 33.8 | V-0 |
| Example 5 | 31.3 | 148 | 33.2 | V-0 |
| Comparative example 1 | 20.9 | 138 | 33.0 | V-0 |
| Comparative example 2 | 30.8 | 146 | 18.9 | V-2 |
| Comparative example 3 | 19.6 | 136 | 18.5 | V-2 |
The data in the analysis table can be obtained, and compared with the polypropylene composite pipe prepared by the non-adding crosslinking component and the polymer halogen-free flame retardant component, the polypropylene composite pipe prepared by the crosslinking component and the polymer halogen-free flame retardant component has more excellent mechanical property, thermal stability and flame retardant property.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
In view of the foregoing, it will be apparent to those skilled in the art from this disclosure that various changes and modifications can be made herein without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.
Claims (3)
1. The preparation process of the modified polypropylene composite pipe is characterized by comprising the following steps of:
first step, mixing materials
Sequentially adding the random copolymer polypropylene, the crosslinking component, the high-molecular halogen-free flame retardant component, the peroxidation initiator, the filler, the compatilizer, the lubricant and the antioxidant auxiliary agent into a high-speed mixer, mixing for 20-30min at a stirring rate of 400-500r/min, and recording the mixture as a premix;
second step, extrusion
Adding the premix into an extruder, setting the temperature of a feeding section of the extruder to 170+/-5 ℃, setting the temperature of a compression section to 190+/-5 ℃, setting the temperature of a plasticizing section to 200+/-5 ℃, setting the temperature of a homogenizing section to 210+/-5 ℃, setting the temperature of a die orifice to 200+/-5 ℃, controlling the rotating speed of a screw to 80-100r/min, and cooling and shaping after melt extrusion to obtain a polypropylene composite pipe;
the preparation process of the polypropylene composite pipe adopts the following raw materials in parts by weight: 75-85 parts of random copolymer polypropylene, 3-6 parts of crosslinking component, 3-5 parts of high polymer halogen-free flame retardant component, 0.5-1 part of peroxidation initiator, 10-15 parts of filler, 10-20 parts of compatilizer, 1-2 parts of lubricant and 0.5-1.5 parts of antioxidant auxiliary agent;
the preparation method of the crosslinking component is as follows:
mixing the dihydroxy-terminated polyphenyl ether and chloroform, adding a mixed catalyst into the formed liquid, stirring for 1-2 hours at room temperature after adding, introducing nitrogen for oxygen removal, adding 5-norbornene-2-carboxylic acid into the mixed liquid, continuously stirring for 4-6 hours at room temperature, pouring into a mixed solution of isopropanol and anhydrous diethyl ether with the volume ratio of 3:7 for precipitation, taking the precipitate, washing for removing impurities, and drying in a vacuum drying oven at 60 ℃ for 8-12 hours to obtain a crosslinking component;
the molecular weight of the dihydroxy-terminated polyphenyl ether is 5000;
the mixed catalyst comprises N-hydroxysuccinimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, wherein the mass ratio is 0.2-0.3:1;
the preparation method of the polymer halogen-free flame retardant component is as follows:
mixing 2, 6-pyridine diformyl chloride with tetrahydrofuran, placing in a polymerization kettle, stirring to form a uniform solution, introducing nitrogen, exhausting air in the polymerization kettle, adding 10- (2, 5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide into the polymerization kettle under the stirring condition, dripping a promoting auxiliary agent, continuously stirring and mixing for 12-18H at room temperature, adding phenol for polymerization inhibition, stirring for 1-2H, evaporating to remove a solvent, taking a solid material, washing to remove impurities, and drying to obtain the high-molecular halogen-free flame retardant component;
the mass ratio of the 2, 6-pyridine dicarboxylic acid dichloride to the 10- (2, 5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide is 1:1.5-1.55;
the promoting auxiliary agent is at least one of triethylamine or pyridine.
2. The process for preparing the modified polypropylene composite pipe according to claim 1, wherein the peroxidation initiator is at least one of benzoyl peroxide and dicumyl peroxide; the filler is a compound of talcum powder and calcium carbonate, and the mass ratio is 1:1; the compatilizer is at least one of maleic anhydride grafted polyethylene or maleic anhydride grafted polypropylene; the lubricant is at least one of calcium stearate, liquid paraffin or polyethylene wax; the antioxidant auxiliary agent is at least one of antioxidant BHT, antioxidant 168 or antioxidant 1076.
3. A modified polypropylene composite pipe, which is characterized by being prepared by the preparation process as claimed in claim 1.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172937A (en) * | 2013-04-11 | 2013-06-26 | 杭州恒标管业有限公司 | Special material for silicane grafted PPR (polypropylene random) pipe and preparation method thereof |
| CN104629175A (en) * | 2015-01-20 | 2015-05-20 | 江苏上上电缆集团有限公司 | Low-smoke halogen-free flame-retardant polypropylene cable material and preparation method thereof |
| CN105348646A (en) * | 2015-12-14 | 2016-02-24 | 湖南工业大学 | Modified polypropylene base low smoke zero halogen cable material and preparing method |
| WO2017083996A1 (en) * | 2015-11-16 | 2017-05-26 | 陈达兵 | Flame resistant antistatic material |
| CN112552602A (en) * | 2019-09-26 | 2021-03-26 | 合肥杰事杰新材料股份有限公司 | Halogen-free flame-retardant polypropylene composite material and preparation method thereof |
| CN113061217A (en) * | 2021-05-13 | 2021-07-02 | 蒋春梅 | Preparation method of novel flame retardant for polylactic acid |
| WO2023020452A1 (en) * | 2021-08-17 | 2023-02-23 | 金发科技股份有限公司 | Halogen-free flame-retardant polypropylene composition, and preparation method therefor and use thereof |
-
2023
- 2023-12-01 CN CN202311631816.XA patent/CN117624789B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172937A (en) * | 2013-04-11 | 2013-06-26 | 杭州恒标管业有限公司 | Special material for silicane grafted PPR (polypropylene random) pipe and preparation method thereof |
| CN104629175A (en) * | 2015-01-20 | 2015-05-20 | 江苏上上电缆集团有限公司 | Low-smoke halogen-free flame-retardant polypropylene cable material and preparation method thereof |
| WO2017083996A1 (en) * | 2015-11-16 | 2017-05-26 | 陈达兵 | Flame resistant antistatic material |
| CN105348646A (en) * | 2015-12-14 | 2016-02-24 | 湖南工业大学 | Modified polypropylene base low smoke zero halogen cable material and preparing method |
| CN112552602A (en) * | 2019-09-26 | 2021-03-26 | 合肥杰事杰新材料股份有限公司 | Halogen-free flame-retardant polypropylene composite material and preparation method thereof |
| CN113061217A (en) * | 2021-05-13 | 2021-07-02 | 蒋春梅 | Preparation method of novel flame retardant for polylactic acid |
| WO2023020452A1 (en) * | 2021-08-17 | 2023-02-23 | 金发科技股份有限公司 | Halogen-free flame-retardant polypropylene composition, and preparation method therefor and use thereof |
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