CN114805980B - A kind of lignin reinforced PE water supply pipe compounding material and preparation method thereof - Google Patents
A kind of lignin reinforced PE water supply pipe compounding material and preparation method thereof Download PDFInfo
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- CN114805980B CN114805980B CN202210384372.3A CN202210384372A CN114805980B CN 114805980 B CN114805980 B CN 114805980B CN 202210384372 A CN202210384372 A CN 202210384372A CN 114805980 B CN114805980 B CN 114805980B
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- lignin
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- water supply
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- 229920005610 lignin Polymers 0.000 title claims abstract description 130
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000000463 material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims description 19
- 238000013329 compounding Methods 0.000 title description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000004970 Chain extender Substances 0.000 claims abstract description 37
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 37
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 239000011347 resin Substances 0.000 claims abstract description 35
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims abstract description 34
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 33
- 125000002091 cationic group Chemical group 0.000 claims abstract description 33
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 33
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 29
- 239000000314 lubricant Substances 0.000 claims abstract description 28
- 239000006229 carbon black Substances 0.000 claims abstract description 27
- -1 aromatic diols Chemical class 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 157
- 239000004698 Polyethylene Substances 0.000 claims description 79
- 238000006243 chemical reaction Methods 0.000 claims description 60
- 238000003756 stirring Methods 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 17
- 239000002244 precipitate Substances 0.000 claims description 17
- 239000003463 adsorbent Substances 0.000 claims description 16
- 239000000378 calcium silicate Substances 0.000 claims description 16
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 16
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical group [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 16
- 229920000573 polyethylene Polymers 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 10
- 238000004537 pulping Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 239000001569 carbon dioxide Substances 0.000 claims description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- DFWZIKINBHKJOB-UHFFFAOYSA-N benzene-1,3-diol;2-(2-hydroxyethoxy)ethanol Chemical compound OCCOCCO.OC1=CC=CC(O)=C1 DFWZIKINBHKJOB-UHFFFAOYSA-N 0.000 claims description 8
- 238000005520 cutting process Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 238000012216 screening Methods 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- WTPYFJNYAMXZJG-UHFFFAOYSA-N 2-[4-(2-hydroxyethoxy)phenoxy]ethanol Chemical compound OCCOC1=CC=C(OCCO)C=C1 WTPYFJNYAMXZJG-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims 7
- ASFLJDMPHLYHLV-UHFFFAOYSA-N lanthanum zinc Chemical compound [Zn].[Zn].[Zn].[Zn].[Zn].[La] ASFLJDMPHLYHLV-UHFFFAOYSA-N 0.000 claims 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 239000003973 paint Substances 0.000 claims 1
- 238000003825 pressing Methods 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- UIPKUCOYESFEMJ-UHFFFAOYSA-N [Zn].[La] Chemical compound [Zn].[La] UIPKUCOYESFEMJ-UHFFFAOYSA-N 0.000 abstract description 27
- 239000002131 composite material Substances 0.000 abstract description 16
- 239000002904 solvent Substances 0.000 abstract description 11
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 33
- 235000006708 antioxidants Nutrition 0.000 description 30
- 239000000203 mixture Substances 0.000 description 21
- 239000012141 concentrate Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 239000007822 coupling agent Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 9
- 239000004615 ingredient Substances 0.000 description 9
- 238000009826 distribution Methods 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 239000005416 organic matter Substances 0.000 description 7
- 239000002530 phenolic antioxidant Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 7
- ADNNZPDVCVMLLS-UHFFFAOYSA-N ethoxysilane 3-triethoxysilylpropan-1-amine Chemical compound NCCC[Si](OCC)(OCC)OCC.C(C)O[SiH3] ADNNZPDVCVMLLS-UHFFFAOYSA-N 0.000 description 6
- 230000000844 anti-bacterial effect Effects 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 229920003002 synthetic resin Polymers 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005189 flocculation Methods 0.000 description 4
- 230000016615 flocculation Effects 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002952 polymeric resin Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ZSUPJEGILVCELX-UHFFFAOYSA-N 3,6-dihydroxycyclohexa-2,4-dien-1-one Chemical compound OC1C=CC(O)=CC1=O ZSUPJEGILVCELX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920005692 JONCRYL® Polymers 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229920001744 Polyaldehyde Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000012445 acidic reagent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 150000002009 diols Chemical group 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000052 poly(p-xylylene) Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明公开了一种木质素增强PE给水管混配料,其包括以下质量份数的组分:树脂100份、改性木质素2~3份、粉体硅烷偶联剂0.5份、增溶剂0.5~1.5份、炭黑0.5~1.5份、芳香族二醇类扩链剂0.2~1份、抗氧化剂0.5~1.5份、润滑剂0.05~0.2份;所述的改性木质素是将黑液浓缩后依次加入双氧水、镧铌酸锌、亚磷酸溶液、阳离子聚丙烯酰胺溶液等进行改性处理得到的;将改性木质素、粉末硅烷偶联剂、增容剂、芳香族二醇类扩链剂、炭黑、抗氧化剂、润滑剂及树脂依次混合后通过挤出、牵引、冷却切割、筛分后得到木质素增强PE给水管混配料。本发明可以有效提升复合材料的拉伸强度、冲击强度等综合机械强度。
The invention discloses a lignin-reinforced PE water supply pipe mixing material, which comprises the following components in parts by mass: 100 parts of resin, 2-3 parts of modified lignin, 0.5 part of powder silane coupling agent, and 0.5 part of solubilizer ~1.5 parts, 0.5~1.5 parts of carbon black, 0.2~1 part of aromatic diol chain extender, 0.5~1.5 parts of antioxidant, 0.05~0.2 parts of lubricant; the modified lignin is concentrated black liquor Then add hydrogen peroxide, zinc lanthanum niobate, phosphorous acid solution, cationic polyacrylamide solution, etc. for modification treatment in sequence; chain extension of modified lignin, powdered silane coupling agent, compatibilizer, and aromatic diols Agents, carbon black, antioxidants, lubricants and resins are mixed in sequence, and then extruded, drawn, cooled, cut, and screened to obtain lignin-reinforced PE water supply pipe mixes. The invention can effectively improve the composite mechanical strength such as tensile strength and impact strength.
Description
技术领域technical field
本发明属于新型管材技术领域,具体涉及一种木质素增强PE给水管混配料及其制备方法。The invention belongs to the technical field of new pipe materials, and in particular relates to a lignin-reinforced PE water supply pipe compounding material and a preparation method thereof.
背景技术Background technique
聚乙烯给水管(PE给水管)作为塑料管道中最具代表的产品,推广和应用正处在平稳上升阶段,但是现有的PE给水管存在以下不足:1)整体抗外压能力较差、遇到坚石、金属碰撞挤压,易引起凹坑,穿孔;2)没有阻燃性;3)对最高使用压力有限制;4)日晒雨淋条件下容易老化,降低使用寿命。Polyethylene water supply pipe (PE water supply pipe) is the most representative product in plastic pipes, and its promotion and application are on the rise. However, the existing PE water supply pipes have the following deficiencies: 1) The overall external pressure resistance is poor, It is easy to cause pits and perforations when encountering solid stones and metal collisions and extrusions; 2) No flame retardancy; 3) There is a limit to the maximum operating pressure; 4) It is easy to age under the sun and rain, reducing the service life.
针对上述问题,目前常规手段是使用碳纤维、植物纤维、合成树脂等有机物对PE给水管进行复合增强,如申请号为CN202010404752.X的中国发明专利申请公开了一种纳米抗菌PE给水管道及其制造工艺,所述纳米抗菌PE给水管道从外至内依次包括由耐磨层、抗紫外层,保温层、抗菌层以及防粘壁层组成;所述纳米抗菌PE给水管道包括按照质量份数组成为:100份高分子树脂、60~70份聚乙烯、8~10份有机化合物热稳定剂、1~3份偶联剂、2~5份苯甲酸脂增塑剂、1~3.5份润滑剂、1~5份抗氧剂;所述耐磨层中各组分的质量份数还包括有:1~5份碳纤维,1~5份碳黑,2~5份纳米碳酸钙,1~3份耐磨剂;所述抗菌层中各组分的质量份数还包括有:1~5份纳米银抗菌母粒,1~5份表面活性剂,1~5份载体。又如申请号为CN202111334714.2的中国发明专利申请公开了一种耐高低温双性能五金卫浴管的制造方法,所述耐高低温双性能五金卫浴管包括合成树脂,稳定剂3-8份、润滑剂5-9份、增塑剂12-17份、耐高温材料2-6份和耐低温材料3-7份;所述耐高温材料可采用硼化物,碳化物,氮化物,硅化物,磷化物和硫化物中的一种或是多种混合物;所述耐低温材料采用聚乙烯、聚四氟乙烯、聚三氟氯乙烯、聚对二甲苯和以环氧粘合的玻璃纤维带中的一种或是多种混合物。In response to the above problems, the current conventional method is to use carbon fibers, plant fibers, synthetic resins and other organic substances to composite PE water supply pipes. For example, the Chinese invention patent application with the application number CN202010404752.X discloses a nano-antibacterial PE water supply pipe and its manufacture. process, the nano antibacterial PE water supply pipeline is composed of a wear-resistant layer, an anti-ultraviolet layer, a thermal insulation layer, an antibacterial layer and an anti-sticking wall layer from the outside to the inside; the nano antibacterial PE water supply pipeline is composed of: 100 parts of polymer resin, 60-70 parts of polyethylene, 8-10 parts of organic compound heat stabilizer, 1-3 parts of coupling agent, 2-5 parts of benzoate plasticizer, 1-3.5 parts of lubricant, 1 ~5 parts of antioxidant; the mass parts of each component in the wear-resistant layer also includes: 1~5 parts of carbon fiber, 1~5 parts of carbon black, 2~5 parts of nano-calcium carbonate, 1~3 parts of anti-oxidant Grinding agent; the mass parts of each component in the antibacterial layer also include: 1-5 parts of nano-silver antibacterial masterbatch, 1-5 parts of surfactant, and 1-5 parts of carrier. Another example is the Chinese invention patent application with the application number CN202111334714.2 disclosing a method for manufacturing a high and low temperature resistant dual-performance hardware sanitary pipe. The high and low temperature resistant dual-performance hardware sanitary pipe includes synthetic resin, 3-8 parts of stabilizer, 5-9 parts of lubricant, 12-17 parts of plasticizer, 2-6 parts of high temperature resistant material and 3-7 parts of low temperature resistant material; the high temperature resistant material can be boride, carbide, nitride, silicide, One or more mixtures of phosphide and sulfide; the low temperature resistant material is made of polyethylene, polytetrafluoroethylene, polytrifluorochloroethylene, parylene and glass fiber tape bonded with epoxy one or more mixtures.
木质素是一种丰富的可再生资源,安全无毒,由刚性的苯丙烷结构单元通过C-O和C-C键相互连接形成的具有三维网状结构的高聚物。现有研究表明,木质素具有高度交联的苯环刚性分子结构,且分子间存在大量的强氢键作用,经过挤出机高温环境下的搅拌和剪切,坚硬的木质素分子充分均匀地分散在PE基体中形成应力集中点,当材料受到长时间的外力作用时能够阻止聚合物分子链构象改变或位移变化而发生的结构性破坏,从而提升了PE管材的抗压强度和抗形变能力。但是,由于木质素与PE两者的极性差别较大,相容性差,木质素与PE在共混时容易在树脂连续相中发生团聚,从而使制备的复合材料力学性能变差,难以实现进一步的工业应用。Lignin is a rich renewable resource, safe and non-toxic, and is a polymer with a three-dimensional network structure formed by rigid phenylpropane structural units connected to each other through C-O and C-C bonds. Existing studies have shown that lignin has a highly cross-linked benzene ring rigid molecular structure, and there are a large number of strong hydrogen bonds between molecules. Dispersed in the PE matrix to form stress concentration points, when the material is subjected to a long-term external force, it can prevent structural damage caused by polymer molecular chain conformation changes or displacement changes, thereby improving the compressive strength and deformation resistance of PE pipes . However, due to the large difference in polarity and poor compatibility between lignin and PE, lignin and PE are prone to agglomeration in the resin continuous phase during blending, which deteriorates the mechanical properties of the prepared composite material and is difficult to achieve. further industrial applications.
发明内容Contents of the invention
针对上述不足,本发明公开了一种木质素增强PE给水管混配料及其制备方法,有效提升复合材料的拉伸强度、冲击强度等综合机械强度。In view of the above shortcomings, the invention discloses a lignin-reinforced PE water supply pipe compounding material and a preparation method thereof, which can effectively improve the comprehensive mechanical strength such as tensile strength and impact strength of the composite material.
本发明是采用如下技术方案实现的:The present invention is realized by adopting the following technical solutions:
一种木质素增强PE给水管混配料,其包括以下质量份数的组分:树脂100份、改性木质素2~3份、粉体硅烷偶联剂0.5份、增溶剂0.5~1.5份、炭黑0.5~1.5份、芳香族二醇类扩链剂0.2~1份、抗氧化剂0.5~1.5份、润滑剂0.05~0.2份;A lignin-reinforced PE water supply pipe mixing material, which includes the following components in parts by mass: 100 parts of resin, 2-3 parts of modified lignin, 0.5 part of powdered silane coupling agent, 0.5-1.5 parts of solubilizer, 0.5-1.5 parts of carbon black, 0.2-1 part of aromatic diol chain extender, 0.5-1.5 parts of antioxidant, 0.05-0.2 part of lubricant;
所述的改性木质素的制备方法包括以下步骤:The preparation method of described modified lignin comprises the following steps:
(1)将碱法制浆得到的黑液浓缩得到固形物含量在20wt%~35wt%的浓缩液;(1) Concentrating the black liquor obtained by alkaline pulping to obtain a concentrated solution with a solid content of 20wt% to 35wt%;
(2)向步骤(1)中得到的浓缩液中依次加入双氧水和镧铌酸锌,然后在80℃~85℃且搅拌速度为300r/min的条件下搅拌反应90min,得到反应液A;(2) Add hydrogen peroxide and zinc lanthanum niobate in sequence to the concentrated solution obtained in step (1), then stir and react for 90 minutes at 80°C to 85°C with a stirring speed of 300r/min to obtain reaction solution A;
(3)将步骤(2)中得到的反应液A冷却至45℃~50℃后恒温,接着向反应液A中通入二氧化碳气体,使得反应液A的pH值达到6.0~6.5,然后再加入亚磷酸溶液,并且在搅拌速度为300r/min的条件下搅拌反应20min,得到反应液B;(3) Cool the reaction solution A obtained in step (2) to 45°C-50°C and keep the temperature constant, then pass carbon dioxide gas into the reaction solution A so that the pH value of the reaction solution A reaches 6.0-6.5, and then add Phosphorous acid solution, and stirring and reacting for 20min under the condition that the stirring speed is 300r/min, obtains the reaction solution B;
(4)将步骤(3)中得到的反应B冷却至室温,接着向反应液B中加入2 wt%的硫酸,使得反应液B的pH值达到2.0~3.0,然后再加入阳离子聚丙烯酰胺溶液,得到絮状沉淀物;(4) Cool the reaction B obtained in step (3) to room temperature, then add 2 wt% sulfuric acid to the reaction solution B to make the pH of the reaction solution B reach 2.0-3.0, and then add the cationic polyacrylamide solution , get flocculent precipitate;
(5)将步骤(4)中得到的絮状沉淀物压滤得到滤渣,然后将滤渣干燥至含水量小于0.5wt%后得到改性木质素。(5) Press-filter the flocculent precipitate obtained in step (4) to obtain a filter residue, and then dry the filter residue until the water content is less than 0.5wt% to obtain the modified lignin.
所述黑液为高浓度的碱性有机废水,含有大量的有机物和无机盐类物质。The black liquor is highly concentrated alkaline organic wastewater containing a large amount of organic matter and inorganic salts.
所述树脂为聚乙烯树脂,且可以为PE125、PE112、PE100和PE80中的任意一种。The resin is polyethylene resin, and can be any one of PE125, PE112, PE100 and PE80.
进一步的,所述镧铌酸锌呈片层状,并且所述镧铌酸锌的化学式为Zn1/2LaNb2O7、Zn1.5La1/3Nb2O7和ZnLa2/3Nb2O7中的任意一种;所述双氧水为30wt%的双氧水;所述阳离子聚丙烯酰胺溶液为5wt%的阳离子聚丙烯酰胺溶液;所述亚磷酸溶液为10wt%~25wt%的亚磷酸水溶液。Further, the zinc lanthanum niobate is in lamellar form, and the chemical formula of the zinc lanthanum niobate is Zn 1/2 LaNb 2 O 7 , Zn 1.5 La 1/3 Nb 2 O 7 and ZnLa 2/3 Nb 2 Any one of O and 7 ; the hydrogen peroxide is 30wt% hydrogen peroxide; the cationic polyacrylamide solution is 5wt% cationic polyacrylamide solution; the phosphorous acid solution is 10wt% to 25wt% phosphorous acid aqueous solution.
进一步的,所述浓缩液与双氧水的体积比为(80~800):1;所述浓缩液的体积与镧铌酸锌的质量比为(5~25)L:1g;所述浓缩液与亚磷酸溶液的体积比为(500~3000):0.1;所述浓缩液与阳离子聚丙烯酰胺溶液的体积比为(1000~2500):0.1。Further, the volume ratio of the concentrated solution to hydrogen peroxide is (80-800):1; the mass ratio of the concentrated solution to zinc lanthanum niobate is (5-25) L:1g; the concentrated solution and The volume ratio of the phosphorous acid solution is (500-3000):0.1; the volume ratio of the concentrated solution to the cationic polyacrylamide solution is (1000-2500):0.1.
进一步的,所述改性木质素的酚羟基含量大于2.5 mmol/g,数均分子量小于11000g/mol。Further, the phenolic hydroxyl content of the modified lignin is greater than 2.5 mmol/g, and the number average molecular weight is less than 11000 g/mol.
进一步的,所述粉末硅烷偶联剂为粉末化的3-氨丙基三乙氧基硅烷,且所述粉末化偶联剂是采用硅质惰性吸附剂为载体吸附粉末化的3-氨丙基三乙氧基硅烷而制成的。Further, the powdered silane coupling agent is powdered 3-aminopropyltriethoxysilane, and the powdered coupling agent adopts a silicon inert adsorbent as a carrier to absorb powdered 3-aminopropyl made from Triethoxysilane.
进一步的,所述硅质惰性吸附剂为硅酸钙,所述硅酸钙的平均孔径为0.8~1.2μm,孔隙率为65~80%,比表面积为250~400 m2/g。Further, the siliceous inert adsorbent is calcium silicate, the calcium silicate has an average pore diameter of 0.8-1.2 μm, a porosity of 65-80%, and a specific surface area of 250-400 m 2 /g.
进一步的,所述炭黑的中位粒径D50小于25 nm,比表面积在500 m2/g以上。Further, the median particle diameter D50 of the carbon black is less than 25 nm, and the specific surface area is above 500 m 2 /g.
进一步的,所述增容剂为苯乙烯-甲基丙烯酸环氧丙酯共聚物;所述芳香族二醇类扩链剂为间苯二酚-双(β-羟乙基)醚和氢醌-双(β-羟乙基)醚中的一种或其任意比例组合;所述抗氧化剂为受阻酚类抗氧剂和亚磷酸酯抗氧剂按照质量比为1.5:1混合而成;所述润滑剂为聚乙烯蜡,优选数均分子量为2000~3000的聚乙烯蜡。Further, the compatibilizer is styrene-glycidyl methacrylate copolymer; the aromatic diol chain extender is resorcinol-bis(β-hydroxyethyl) ether and hydroquinone - one of two (β-hydroxyethyl) ethers or a combination thereof in any proportion; the antioxidant is mixed with a hindered phenolic antioxidant and a phosphite antioxidant according to a mass ratio of 1.5:1; the The lubricant is polyethylene wax, preferably a polyethylene wax with a number average molecular weight of 2000 to 3000.
本发明的技术原理为:Technical principle of the present invention is:
由于木质素是聚酚类高分子化合物,大量的活性基团包裹在分子内部,分子间相互作用强,芳环结构交织成网,与碳酸钙、滑石等常规树脂填充料相比,木质素与硬脂酸、硅烷、和铝酸酯等常规表面改性剂的反应活性差。因此,本发明首先通过在碱性条件下,以H2O2为氧化剂,镧铌酸锌为催化剂,高效催化木质素解聚为系列低分子量、多醛基结构的分子链段;随后用二氧化碳对溶液进行中和处理后,以亚磷酸催化醛基还原,形成多羟基的小分子木质素链段,从而提高木质素与高分子树脂的相容性以及其与常规偶联剂、增容剂和扩链剂的反应活性;此时,由于木质素链段在中性溶液中存在一定的水溶性,需要进一步用H2SO4对溶液进行酸化,使木质素分子链段充分析出,并辅以一定量的絮凝剂使其更容易沉淀,实现固液分离。Since lignin is a polyphenolic macromolecular compound, a large number of active groups are wrapped inside the molecule, the intermolecular interaction is strong, and the aromatic ring structure is interwoven into a network. Compared with conventional resin fillers such as calcium carbonate and talc, lignin and Conventional surface modifiers such as stearic acid, silanes, and aluminates have poor reactivity. Therefore, the present invention firstly depolymerizes lignin into a series of molecular segments with low molecular weight and polyaldehyde structure by using H 2 O 2 as an oxidant and zinc lanthanum niobate as a catalyst under alkaline conditions; After the solution is neutralized, phosphorous acid is used to catalyze the reduction of aldehyde groups to form polyhydroxyl small molecular lignin segments, thereby improving the compatibility of lignin with polymer resins and its compatibility with conventional coupling agents and compatibilizers. Reactivity with the chain extender; at this time, because the lignin segment has a certain water solubility in the neutral solution, it is necessary to further acidify the solution with H 2 SO 4 to fully analyze the lignin molecular segment and assist A certain amount of flocculant makes it easier to settle and realize solid-liquid separation.
同时,本发明还选择性加入增溶剂、扩链剂等组分,一方面进一步改善木质素和高分子树脂间的相容性,另一方面,经本发明方法得到的改性木质素,其分子链段上存在大量的活性羟基,添加适合的具有反应性的扩链剂,可以进一步增加木质素与PE间的结合力,将部分没能与偶联剂反应的、残存的活性羟基,通过扩链剂的桥接作用,以化学键形式与PE树脂连接起来,从而提高复合材料的综合性能。At the same time, the present invention also selectively adds components such as solubilizers and chain extenders, on the one hand to further improve the compatibility between lignin and polymer resins, on the other hand, the modified lignin obtained by the method of the present invention, its There are a large number of active hydroxyl groups on the molecular chain segment. Adding a suitable reactive chain extender can further increase the binding force between lignin and PE, and part of the remaining active hydroxyl groups that have not reacted with the coupling agent can be passed through The bridging effect of the chain extender connects the PE resin in the form of a chemical bond, thereby improving the comprehensive performance of the composite material.
上述木质素增强PE给水管混配料的制备方法,其包括以下步骤:The preparation method of the above-mentioned lignin-enhanced PE water supply pipe mixing material comprises the following steps:
S1、将改性木质素加入到高速混合机中,以500 r/min的速度搅拌,当温度达到80~110℃后,加入粉末硅烷偶联剂混合3 min,接着再加入增容剂继续混合5~10min,然后升温至140℃,再加入芳香族二醇类扩链剂混合5min,接着依次加入炭黑、抗氧化剂、润滑剂及树脂后,搅拌处理10~12min得到混合物料;S1. Add the modified lignin to the high-speed mixer and stir at a speed of 500 r/min. When the temperature reaches 80-110°C, add the powdered silane coupling agent and mix for 3 minutes, then add the compatibilizer and continue mixing 5-10 minutes, then heat up to 140°C, add aromatic diol chain extender and mix for 5 minutes, then add carbon black, antioxidant, lubricant and resin in sequence, and stir for 10-12 minutes to obtain the mixed material;
S2、将步骤S1中得到的混合物料通过进料口加入到螺杆挤出机中处理后,在通过牵引、冷却切割、筛分后得到木质素增强PE给水管混配料。S2. Add the mixed material obtained in step S1 into the screw extruder through the feed port for processing, and obtain the lignin-reinforced PE water supply pipe mixed material after traction, cooling, cutting and screening.
进一步的,在步骤S2中,所述螺杆挤出机中螺杆直径为71mm,螺槽比值为1.5,螺槽深度为14mm,螺杆长径比为40/1,螺杆共分10个加热区,从进料端开始10个加热区的温度依次为135℃、145℃、150℃、155℃、160℃、165℃、170℃、160℃、150℃、140℃;螺杆转速为500rpm。Further, in step S2, the screw diameter in the screw extruder is 71 mm, the screw groove ratio is 1.5, the screw groove depth is 14 mm, the screw length-to-diameter ratio is 40/1, and the screw is divided into 10 heating zones. The temperature of the 10 heating zones starting from the feed end is 135°C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, 160°C, 150°C, 140°C; the screw speed is 500rpm.
本技术方案与现有技术相比较具有以下有益效果:Compared with the prior art, this technical solution has the following beneficial effects:
1、常规木质素催化氧化,一般需要在超过200℃反应2~5h以上才能获得较好的产物。本发明采用低温碱条件氧化法,以H2O2为氧化剂,镧铌酸锌为催化剂,在80 ℃~85 ℃下反应20 min即可获得低分子量、高活性的木质素分子链段;同时,相对未改性的木质素大分子,本发明得到的多羟基木质素分子链段更易于与硅烷偶联剂、相容剂和扩链剂发生反应,表现出更加优异的热流动性、树脂相容性和反应活性。1. Conventional lignin catalytic oxidation generally needs to be reacted at over 200°C for more than 2~5h to obtain better products. The present invention adopts a low-temperature alkaline oxidation method, using H 2 O 2 as an oxidant, and zinc lanthanum niobate as a catalyst, and reacting at 80°C to 85°C for 20 minutes can obtain low-molecular-weight, high-activity lignin molecular segments; at the same time , compared with unmodified lignin macromolecules, the polyhydroxy lignin molecular segments obtained in the present invention are more likely to react with silane coupling agents, compatibilizers and chain extenders, showing more excellent thermal fluidity, resin compatibility and reactivity.
2、本发明是直接采用碱法制浆黑液作为原料来源,可减少黑液对环境的污染,并实现了木质素的资源化再生利用;同时,本发明采用二氧化碳作为酸性试剂中和反应体系的碱度,在节约酸的同时,在一定程度上也达到碳中和目的。2. The present invention directly uses alkaline pulping black liquor as a raw material source, which can reduce the pollution of black liquor to the environment, and realizes the resource recycling and utilization of lignin; at the same time, the present invention uses carbon dioxide as an acidic reagent to neutralize the reaction system Alkalinity, while saving acid, also achieves the purpose of carbon neutrality to a certain extent.
3、本发明采用粉末状的偶联剂作为木质素的疏水化改性剂,可以有效改善液体状硅烷偶联剂在木质素分子上粘团而分散不均匀的问题,从而提升木质素的疏水化改性程度。同时,通过添加具有苯环结构的反应型增容剂PS-co-GMA,可以改善以苯丙烷为基本结构单元的木质素与PE树脂间的界面相容性,同时通过增加具有反应性的芳香族二醇类扩链剂,可以将木质素分子链段中的活性羟基与PE树脂链接为一体,进而有效提升复合材料的拉伸强度、冲击强度等综合机械强度。3. The present invention uses a powdery coupling agent as a hydrophobic modifier of lignin, which can effectively improve the problem of uneven dispersion of liquid silane coupling agents on lignin molecules, thereby improving the hydrophobicity of lignin. degree of modification. At the same time, by adding the reactive compatibilizer PS-co-GMA with benzene ring structure, the interfacial compatibility between lignin with phenylpropane as the basic structural unit and PE resin can be improved, and by increasing the reactive aromatic The family diol chain extender can link the active hydroxyl group in the lignin molecular chain segment with the PE resin, thereby effectively improving the comprehensive mechanical strength of the composite material such as tensile strength and impact strength.
附图说明Description of drawings
图1是实施例1中得到的改性木质素的SEM图。FIG. 1 is an SEM image of the modified lignin obtained in Example 1.
图2是对比例1中得到的原木质素和实施例1中得到的改性木质素的GPC图,其中曲线1表示原木质素,曲线2表示改性木质素。Fig. 2 is a GPC graph of the original lignin obtained in Comparative Example 1 and the modified lignin obtained in Example 1, wherein curve 1 represents the original lignin, and
图3是对比例1中得到的原木质素和实施例1中得到的改性木质素的DSC图,其中曲线1表示原木质素,曲线2表示改性木质素。Fig. 3 is a DSC diagram of the original lignin obtained in Comparative Example 1 and the modified lignin obtained in Example 1, wherein curve 1 represents the original lignin, and
图4是实验例中按照实施例1所述方法制备得到的混配料样条的脆断面的SEM图。Fig. 4 is an SEM image of the brittle section of the mixed material sample prepared according to the method described in Example 1 in the experimental example.
图5是实验例中按照对比例1所述方法制备得到的混配料样条的脆断面的SEM图。Fig. 5 is an SEM image of the brittle section of the mixed material sample prepared according to the method described in Comparative Example 1 in the experimental example.
图6是实验例中按照实施例1、对比例1和对比例9中所述方法制备得到的混配料样条的拉伸强度-断裂伸长率测试曲线图,其中曲线1表示实施例1中混配料样条,曲线2表示曲线2表示对比1中混配料样条,曲线3表示对比例9中混配料样条。Fig. 6 is the tensile strength-elongation at break test curve figure of the compound sample prepared according to the method described in embodiment 1, comparative example 1 and comparative example 9 in the experimental example, wherein curve 1 represents that in embodiment 1 Mixed material spline,
具体实施方式Detailed ways
以下通过实施例进一步说明本发明,但不作为对本发明的限制。下列实施例中未注明的具体实验条件和方法,所采用的技术手段通常为本领域技术人员所熟知的常规手段。The present invention is further illustrated by the following examples, but not as a limitation of the present invention. For the specific experimental conditions and methods not indicated in the following examples, the technical means used are generally conventional means well known to those skilled in the art.
实施例1:Example 1:
一种木质素增强PE给水管混配料,其包括以下质量份数的组分:树脂100份、改性木质素2份、粉体硅烷偶联剂0.5份、增溶剂0.85份、炭黑0.75份、芳香族二醇类扩链剂0.8份、抗氧化剂1.0份、润滑剂0.15份;所述黑液为高浓度的碱性有机废水,含有大量的有机物和无机盐类物质;所述树脂为PE125;所述粉末硅烷偶联剂为粉末化的3-氨丙基三乙氧基硅烷,且所述粉末化偶联剂是采用硅质惰性吸附剂为载体吸附粉末化的3-氨丙基三乙氧基硅烷而制成的;所述硅质惰性吸附剂为硅酸钙,所述硅酸钙的平均孔径为1.02μm,孔隙率为72.3%,比表面积为287.1 m2/g;所述炭黑的中位粒径D50为20 nm,比表面积在1200m2/g;所述增容剂为苯乙烯-甲基丙烯酸环氧丙酯共聚物;所述芳香族二醇类扩链剂为间苯二酚-双(β-羟乙基)醚和氢醌-双(β-羟乙基)醚按照质量比为7:3混合得到的;所述抗氧化剂为受阻酚类抗氧剂和亚磷酸酯抗氧剂按照质量比为1.5:1混合而成;所述润滑剂是数均分子量为3000的聚乙烯蜡;A lignin-reinforced PE water supply pipe compounding material, which includes the following components in parts by mass: 100 parts of resin, 2 parts of modified lignin, 0.5 part of powdered silane coupling agent, 0.85 part of solubilizer, and 0.75 part of carbon black , 0.8 part of aromatic diol chain extender, 1.0 part of antioxidant, 0.15 part of lubricant; the black liquor is alkaline organic wastewater with high concentration, containing a large amount of organic matter and inorganic salts; the resin is PE125 ; The powdered silane coupling agent is powdered 3-aminopropyltriethoxysilane, and the powdered coupling agent adopts a silicon inert adsorbent as a carrier to absorb powdered 3-aminopropyltriethoxysilane ethoxysilane; the siliceous inert adsorbent is calcium silicate, the average pore diameter of the calcium silicate is 1.02 μm, the porosity is 72.3%, and the specific surface area is 287.1 m 2 /g; The median particle size D50 of carbon black is 20 nm, and the specific surface area is 1200m 2 /g; the compatibilizer is styrene-glycidyl methacrylate copolymer; the aromatic diol chain extender is Resorcinol-bis(β-hydroxyethyl) ether and hydroquinone-bis(β-hydroxyethyl) ether are obtained by mixing according to the mass ratio of 7:3; the antioxidant is hindered phenolic antioxidant and The phosphite antioxidant is mixed according to the mass ratio of 1.5:1; the lubricant is a polyethylene wax with a number average molecular weight of 3000;
所述的改性木质素的制备方法包括以下步骤:The preparation method of described modified lignin comprises the following steps:
(1)将碱法制浆得到的黑液浓缩得到固形物含量在30wt%的浓缩液;(1) Concentrating the black liquor obtained by alkaline pulping to obtain a concentrated solution with a solid content of 30wt%;
(2)向步骤(1)中得到的浓缩液中依次加入双氧水和镧铌酸锌,然后在82℃且搅拌速度为300r/min的条件下搅拌反应90min,得到反应液A;所述镧铌酸锌呈片层状,并且所述镧铌酸锌的化学式为Zn1/2LaNb2O7;所述双氧水为30wt%的双氧水;所述浓缩液与双氧水的体积比为1000:5;所述浓缩液的体积与镧铌酸锌的质量比为1000L:75g;(2) Add hydrogen peroxide and zinc lanthanum niobate successively to the concentrated solution obtained in step (1), then stir and react at 82°C and a stirring speed of 300r/min for 90min to obtain reaction solution A; the lanthanum niobium Zinc acid is lamellar, and the chemical formula of zinc lanthanum niobate is Zn 1/2 LaNb 2 O 7 ; the hydrogen peroxide is 30wt% hydrogen peroxide; the volume ratio of the concentrate to hydrogen peroxide is 1000:5; The volume of described concentrate and the mass ratio of zinc lanthanum niobate are 1000L:75g;
(3)将步骤(2)中得到的反应液A冷却至45℃后恒温,接着向反应液A中通入二氧化碳气体,使得反应液A的pH值达到6.2,然后再加入亚磷酸溶液,并且在搅拌速度为300r/min的条件下搅拌反应20min,得到反应液B;所述浓缩液与亚磷酸溶液的体积比为1000:0.1;所述亚磷酸溶液为,20wt%的亚磷酸水溶液;(3) Cool the reaction solution A obtained in step (2) to 45°C and keep the temperature constant, then pass carbon dioxide gas into the reaction solution A, so that the pH value of the reaction solution A reaches 6.2, and then add the phosphorous acid solution, and Stirring and reacting for 20 minutes at a stirring speed of 300r/min to obtain a reaction solution B; the volume ratio of the concentrated solution to the phosphorous acid solution is 1000:0.1; the phosphorous acid solution is a 20wt% phosphorous acid aqueous solution;
(4)将步骤(3)中得到的反应B冷却至室温,接着向反应液B中加入2 wt%的硫酸,使得反应液B的pH值达到2.5,然后再加入阳离子聚丙烯酰胺溶液,得到絮状沉淀物;所述阳离子聚丙烯酰胺溶液为5wt%的阳离子聚丙烯酰胺溶液;所述浓缩液与阳离子聚丙烯酰胺溶液的体积比为1000:0.08;(4) Cool the reaction B obtained in step (3) to room temperature, then add 2 wt% sulfuric acid to the reaction solution B, so that the pH value of the reaction solution B reaches 2.5, and then add the cationic polyacrylamide solution to obtain Flocculent precipitates; the cationic polyacrylamide solution is a 5wt% cationic polyacrylamide solution; the volume ratio of the concentrated solution to the cationic polyacrylamide solution is 1000:0.08;
(5)将步骤(4)中得到的絮状沉淀物压滤得到滤渣,然后将滤渣干燥至含水量小于0.5wt%后得到改性木质素。(5) Press-filter the flocculent precipitate obtained in step (4) to obtain a filter residue, and then dry the filter residue until the water content is less than 0.5wt% to obtain the modified lignin.
本实施例所述木质素增强PE给水管混配料的制备方法,其包括以下步骤:The preparation method of the lignin-enhanced PE water supply pipe mixing material described in this embodiment comprises the following steps:
S1、将改性木质素加入到高速混合机中,以500 r/min的速度搅拌,当温度达到105℃后,加入粉末硅烷偶联剂混合3 min,接着再加入增容剂继续混合5min,然后升温至140℃,再加入芳香族二醇类扩链剂混合5min,接着依次加入炭黑、抗氧化剂、润滑剂及树脂后,搅拌处理11min得到混合物料;S1. Add the modified lignin to the high-speed mixer and stir at a speed of 500 r/min. When the temperature reaches 105°C, add powdered silane coupling agent and mix for 3 minutes, then add compatibilizer and continue mixing for 5 minutes. Then heat up to 140°C, add aromatic diol chain extender and mix for 5 minutes, then add carbon black, antioxidant, lubricant and resin in sequence, and stir for 11 minutes to obtain the mixed material;
S2、将步骤S1中得到的混合物料通过进料口加入到螺杆挤出机中处理后,在通过牵引、冷却切割、筛分后得到木质素增强PE给水管混配料;所述螺杆挤出机中螺杆直径为71mm,螺槽比值为1.5,螺槽深度为14mm,螺杆长径比为40/1,螺杆共分10个加热区,从进料端开始10个加热区的温度依次为135℃、145℃、150℃、155℃、160℃、165℃、170℃、160℃、150℃、140℃;螺杆转速为500rpm。S2. Add the mixed material obtained in step S1 to the screw extruder through the feed port for processing, and obtain lignin-enhanced PE water supply pipe mixed ingredients after traction, cooling, cutting, and screening; the screw extruder The diameter of the middle screw is 71mm, the ratio of the screw groove is 1.5, the depth of the screw groove is 14mm, the ratio of length to diameter of the screw is 40/1, the screw is divided into 10 heating zones, and the temperature of the 10 heating zones starting from the feed end is 135°C , 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, 160°C, 150°C, 140°C; the screw speed is 500rpm.
实施例2:Example 2:
一种木质素增强PE给水管混配料,其包括以下质量份数的组分:树脂100份、改性木质素3份、粉体硅烷偶联剂0.5份、增溶剂0.5份、炭黑0.85份、芳香族二醇类扩链剂0.3份、抗氧化剂1.0份、润滑剂0.1份;所述黑液为高浓度的碱性有机废水,含有大量的有机物和无机盐类物质;所述树脂为PE100;所述粉末硅烷偶联剂为粉末化的3-氨丙基三乙氧基硅烷,且所述粉末化偶联剂是采用硅质惰性吸附剂为载体吸附粉末化的3-氨丙基三乙氧基硅烷而制成的;所述硅质惰性吸附剂为硅酸钙,所述硅酸钙的平均孔径为1.2μm,孔隙率为68.8%,比表面积为205.0 m2/g;所述炭黑的中位粒径D50为25 nm,比表面积在925.3 m2/g;所述增容剂为苯乙烯-甲基丙烯酸环氧丙酯共聚物;所述芳香族二醇类扩链剂为间苯二酚-双(β-羟乙基)醚和氢醌-双(β-羟乙基)醚按照质量比为1:1混合得到的;所述抗氧化剂为受阻酚类抗氧剂和亚磷酸酯抗氧剂按照质量比为1.5:1混合而成;所述润滑剂是数均分子量为3000的聚乙烯蜡;A lignin-reinforced PE water supply pipe compounding material, which includes the following components in parts by mass: 100 parts of resin, 3 parts of modified lignin, 0.5 part of powdered silane coupling agent, 0.5 part of solubilizer, and 0.85 part of carbon black , 0.3 parts of aromatic diol chain extenders, 1.0 parts of antioxidants, and 0.1 parts of lubricants; the black liquor is high-concentration alkaline organic wastewater containing a large amount of organic matter and inorganic salts; the resin is PE100 ; The powdered silane coupling agent is powdered 3-aminopropyltriethoxysilane, and the powdered coupling agent adopts a silicon inert adsorbent as a carrier to absorb powdered 3-aminopropyltriethoxysilane ethoxysilane; the siliceous inert adsorbent is calcium silicate, the average pore diameter of the calcium silicate is 1.2 μm, the porosity is 68.8%, and the specific surface area is 205.0 m 2 /g; The median particle size D50 of carbon black is 25 nm, and the specific surface area is 925.3 m 2 /g; the compatibilizer is styrene-glycidyl methacrylate copolymer; the aromatic diol chain extender It is obtained by mixing resorcinol-bis(β-hydroxyethyl) ether and hydroquinone-bis(β-hydroxyethyl) ether according to the mass ratio of 1:1; the antioxidant is hindered phenolic antioxidant It is mixed with a phosphite antioxidant according to a mass ratio of 1.5:1; the lubricant is a polyethylene wax with a number average molecular weight of 3000;
所述的改性木质素的制备方法包括以下步骤:The preparation method of described modified lignin comprises the following steps:
(1)将碱法制浆得到的黑液浓缩得到固形物含量在35wt%的浓缩液;(1) Concentrating the black liquor obtained by alkaline pulping to obtain a concentrated solution with a solid content of 35wt%;
(2)向步骤(1)中得到的浓缩液中依次加入双氧水和镧铌酸锌,然后在80℃且搅拌速度为300r/min的条件下搅拌反应90min,得到反应液A;所述镧铌酸锌呈片层状,并且所述镧铌酸锌的化学式为ZnLa2/3Nb2O7;所述双氧水为30wt%的双氧水;所述浓缩液与双氧水的体积比为1200:4;所述浓缩液的体积与镧铌酸锌的质量比为1200L:50g;(2) Add hydrogen peroxide and zinc lanthanum niobate successively to the concentrated solution obtained in step (1), then stir and react at 80°C and a stirring speed of 300r/min for 90min to obtain reaction solution A; the lanthanum niobium Zinc acid is lamellar, and the chemical formula of zinc lanthanum niobate is ZnLa 2/3 Nb 2 O 7 ; the hydrogen peroxide is 30wt% hydrogen peroxide; the volume ratio of the concentrate to hydrogen peroxide is 1200:4; The volume of described concentrate and the mass ratio of zinc lanthanum niobate are 1200L: 50g;
(3)将步骤(2)中得到的反应液A冷却至45℃~50℃后恒温,接着向反应液A中通入二氧化碳气体,使得反应液A的pH值达到6.0~6.5,然后再加入亚磷酸溶液,并且在搅拌速度为300r/min的条件下搅拌反应20min,得到反应液B;所述浓缩液与亚磷酸溶液的体积比为1200:0.12;所述亚磷酸溶液为25wt%的亚磷酸水溶液;(3) Cool the reaction solution A obtained in step (2) to 45°C-50°C and keep the temperature constant, then pass carbon dioxide gas into the reaction solution A so that the pH value of the reaction solution A reaches 6.0-6.5, and then add Phosphorous acid solution, and stirring reaction 20min under the condition of 300r/min at stirring speed, obtain reaction solution B; The volume ratio of described concentrated solution and phosphorous acid solution is 1200:0.12; Described phosphorous acid solution is the phosphorous acid solution of 25wt%. Phosphoric acid aqueous solution;
(4)将步骤(3)中得到的反应B冷却至室温,接着向反应液B中加入2 wt%的硫酸,使得反应液B的pH值达到3.0,然后再加入阳离子聚丙烯酰胺溶液,得到絮状沉淀物;所述阳离子聚丙烯酰胺溶液为5wt%的阳离子聚丙烯酰胺溶液;所述浓缩液与阳离子聚丙烯酰胺溶液的体积比为1200:0.08;(4) Cool the reaction B obtained in step (3) to room temperature, then add 2 wt% sulfuric acid to the reaction solution B, so that the pH value of the reaction solution B reaches 3.0, and then add the cationic polyacrylamide solution to obtain Flocculent precipitate; the cationic polyacrylamide solution is a 5wt% cationic polyacrylamide solution; the volume ratio of the concentrated solution to the cationic polyacrylamide solution is 1200:0.08;
(5)将步骤(4)中得到的絮状沉淀物压滤得到滤渣,然后将滤渣干燥至含水量小于0.5wt%后得到改性木质素。(5) Press-filter the flocculent precipitate obtained in step (4) to obtain a filter residue, and then dry the filter residue until the water content is less than 0.5wt% to obtain the modified lignin.
本实施例所述木质素增强PE给水管混配料的制备方法,其包括以下步骤:The preparation method of the lignin-enhanced PE water supply pipe mixing material described in this embodiment comprises the following steps:
S1、将改性木质素加入到高速混合机中,以500 r/min的速度搅拌,当温度达到110℃后,加入粉末硅烷偶联剂混合3 min,接着再加入增容剂继续混合7min,然后升温至140℃,再加入芳香族二醇类扩链剂混合5min,接着依次加入炭黑、抗氧化剂、润滑剂及树脂后,搅拌处理10.5min得到混合物料;S1. Add the modified lignin to the high-speed mixer and stir at a speed of 500 r/min. When the temperature reaches 110°C, add powdered silane coupling agent and mix for 3 minutes, then add compatibilizer and continue mixing for 7 minutes. Then heat up to 140°C, add aromatic diol chain extender and mix for 5 minutes, then add carbon black, antioxidant, lubricant and resin in sequence, and stir for 10.5 minutes to obtain the mixed material;
S2、将步骤S1中得到的混合物料通过进料口加入到螺杆挤出机中处理后,在通过牵引、冷却切割、筛分后得到木质素增强PE给水管混配料;所述螺杆挤出机中螺杆直径为71mm,螺槽比值为1.5,螺槽深度为14mm,螺杆长径比为40/1,螺杆共分10个加热区,从进料端开始10个加热区的温度依次为135℃、145℃、150℃、155℃、160℃、165℃、170℃、160℃、150℃、140℃;螺杆转速为500rpm。S2. Add the mixed material obtained in step S1 to the screw extruder through the feed port for processing, and obtain lignin-enhanced PE water supply pipe mixed ingredients after traction, cooling, cutting, and screening; the screw extruder The diameter of the middle screw is 71mm, the ratio of the screw groove is 1.5, the depth of the screw groove is 14mm, the ratio of length to diameter of the screw is 40/1, the screw is divided into 10 heating zones, and the temperature of the 10 heating zones starting from the feed end is 135°C , 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, 160°C, 150°C, 140°C; the screw speed is 500rpm.
实施例3:Example 3:
一种木质素增强PE给水管混配料,其包括以下质量份数的组分:树脂100份、改性木质素2份、粉体硅烷偶联剂0.5份、增溶剂0.9份、炭黑1.25份、芳香族二醇类扩链剂0.2份、抗氧化剂1.25份、润滑剂0.2份;所述黑液为高浓度的碱性有机废水,含有大量的有机物和无机盐类物质;所述树脂为PE112;所述粉末硅烷偶联剂为粉末化的3-氨丙基三乙氧基硅烷,且所述粉末化偶联剂是采用硅质惰性吸附剂为载体吸附粉末化的3-氨丙基三乙氧基硅烷而制成的;所述硅质惰性吸附剂为硅酸钙,所述硅酸钙的平均孔径为0.8μm,孔隙率为80%,比表面积为289.36m2/g;所述炭黑的中位粒径D50为10 nm,比表面积在800 m2/g;所述增容剂为苯乙烯-甲基丙烯酸环氧丙酯共聚物;所述芳香族二醇类扩链剂为间苯二酚-双(β-羟乙基)醚和氢醌-双(β-羟乙基)醚按照质量比为1:4混合得到的;所述抗氧化剂为受阻酚类抗氧剂和亚磷酸酯抗氧剂按照质量比为1.5:1混合而成;所述润滑剂是数均分子量为3000的聚乙烯蜡;A lignin-reinforced PE water supply pipe compounding material, which includes the following components in parts by mass: 100 parts of resin, 2 parts of modified lignin, 0.5 part of powdered silane coupling agent, 0.9 part of solubilizer, and 1.25 parts of carbon black , 0.2 part of aromatic diol chain extender, 1.25 part of antioxidant, 0.2 part of lubricant; the black liquor is alkaline organic wastewater with high concentration, containing a large amount of organic matter and inorganic salts; the resin is PE112 ; The powdered silane coupling agent is powdered 3-aminopropyltriethoxysilane, and the powdered coupling agent adopts a silicon inert adsorbent as a carrier to absorb powdered 3-aminopropyltriethoxysilane ethoxysilane; the siliceous inert adsorbent is calcium silicate, the average pore diameter of the calcium silicate is 0.8 μm, the porosity is 80%, and the specific surface area is 289.36m 2 /g; The median particle size D50 of carbon black is 10 nm, and the specific surface area is 800 m 2 /g; the compatibilizer is styrene-glycidyl methacrylate copolymer; the aromatic diol chain extender It is obtained by mixing resorcinol-bis(β-hydroxyethyl) ether and hydroquinone-bis(β-hydroxyethyl) ether according to the mass ratio of 1:4; the antioxidant is hindered phenolic antioxidant It is mixed with a phosphite antioxidant according to a mass ratio of 1.5:1; the lubricant is a polyethylene wax with a number average molecular weight of 3000;
所述的改性木质素的制备方法包括以下步骤:The preparation method of described modified lignin comprises the following steps:
(1)将碱法制浆得到的黑液浓缩得到固形物含量在35wt%的浓缩液;(1) Concentrating the black liquor obtained by alkaline pulping to obtain a concentrated solution with a solid content of 35wt%;
(2)向步骤(1)中得到的浓缩液中依次加入双氧水和镧铌酸锌,然后在80℃且搅拌速度为300r/min的条件下搅拌反应90min,得到反应液A;所述镧铌酸锌呈片层状,并且所述镧铌酸锌的化学式为Zn1.5La1/3Nb2O7;所述双氧水为30wt%的双氧水;所述浓缩液与双氧水的体积比为80:1;所述浓缩液的体积与镧铌酸锌的质量比为800L:150g;(2) Add hydrogen peroxide and zinc lanthanum niobate successively to the concentrated solution obtained in step (1), then stir and react at 80°C and a stirring speed of 300r/min for 90min to obtain reaction solution A; the lanthanum niobium Zinc acid is lamellar, and the chemical formula of zinc lanthanum niobate is Zn 1.5 La 1/3 Nb 2 O 7 ; the hydrogen peroxide is 30wt% hydrogen peroxide; the volume ratio of the concentrate to hydrogen peroxide is 80:1 ; The volume of the concentrate and the mass ratio of zinc lanthanum niobate are 800L: 150g;
(3)将步骤(2)中得到的反应液A冷却至50℃后恒温,接着向反应液A中通入二氧化碳气体,使得反应液A的pH值达到6.0,然后再加入亚磷酸溶液,并且在搅拌速度为300r/min的条件下搅拌反应20min,得到反应液B;所述浓缩液与亚磷酸溶液的体积比为800:0.03;所述亚磷酸溶液为10wt%的亚磷酸水溶液;(3) Cool the reaction solution A obtained in step (2) to 50°C and then keep the temperature constant, then pass carbon dioxide gas into the reaction solution A, so that the pH value of the reaction solution A reaches 6.0, and then add the phosphorous acid solution, and Stirring and reacting for 20min at a stirring speed of 300r/min to obtain a reaction solution B; the volume ratio of the concentrated solution to the phosphorous acid solution is 800:0.03; the phosphorous acid solution is a 10wt% phosphorous acid aqueous solution;
(4)将步骤(3)中得到的反应B冷却至室温,接着向反应液B中加入2 wt%的硫酸,使得反应液B的pH值达到2.0,然后再加入阳离子聚丙烯酰胺溶液,得到絮状沉淀物;所述阳离子聚丙烯酰胺溶液为5wt%的阳离子聚丙烯酰胺溶液;所述浓缩液与阳离子聚丙烯酰胺溶液的体积比为800:0.08;(4) Cool the reaction B obtained in step (3) to room temperature, then add 2 wt% sulfuric acid to the reaction solution B, so that the pH value of the reaction solution B reaches 2.0, and then add the cationic polyacrylamide solution to obtain Flocculent precipitate; the cationic polyacrylamide solution is a 5wt% cationic polyacrylamide solution; the volume ratio of the concentrated solution to the cationic polyacrylamide solution is 800:0.08;
(5)将步骤(4)中得到的絮状沉淀物压滤得到滤渣,然后将滤渣干燥至含水量小于0.5wt%后得到改性木质素。(5) Press-filter the flocculent precipitate obtained in step (4) to obtain a filter residue, and then dry the filter residue until the water content is less than 0.5wt% to obtain the modified lignin.
本实施例所述木质素增强PE给水管混配料的制备方法,其包括以下步骤:The preparation method of the lignin-enhanced PE water supply pipe mixing material described in this embodiment comprises the following steps:
S1、将改性木质素加入到高速混合机中,以500 r/min的速度搅拌,当温度达到95℃后,加入粉末硅烷偶联剂混合3 min,接着再加入增容剂继续混合10min,然后升温至140℃,再加入芳香族二醇类扩链剂混合5min,接着依次加入炭黑、抗氧化剂、润滑剂及树脂后,搅拌处理10min得到混合物料;S1. Add the modified lignin to the high-speed mixer and stir at a speed of 500 r/min. When the temperature reaches 95°C, add the powdered silane coupling agent and mix for 3 minutes, then add the compatibilizer and continue mixing for 10 minutes. Then heat up to 140°C, add aromatic diol chain extender and mix for 5 minutes, then add carbon black, antioxidant, lubricant and resin in sequence, and stir for 10 minutes to obtain the mixed material;
S2、将步骤S1中得到的混合物料通过进料口加入到螺杆挤出机中处理后,在通过牵引、冷却切割、筛分后得到木质素增强PE给水管混配料;所述螺杆挤出机中螺杆直径为71mm,螺槽比值为1.5,螺槽深度为14mm,螺杆长径比为40/1,螺杆共分10个加热区,从进料端开始10个加热区的温度依次为135℃、145℃、150℃、155℃、160℃、165℃、170℃、160℃、150℃、140℃;螺杆转速为500rpm。S2. Add the mixed material obtained in step S1 to the screw extruder through the feed port for processing, and obtain lignin-enhanced PE water supply pipe mixed ingredients after traction, cooling, cutting, and screening; the screw extruder The diameter of the middle screw is 71mm, the ratio of the screw groove is 1.5, the depth of the screw groove is 14mm, the ratio of length to diameter of the screw is 40/1, the screw is divided into 10 heating zones, and the temperature of the 10 heating zones starting from the feed end is 135°C , 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, 160°C, 150°C, 140°C; the screw speed is 500rpm.
实施例4:Example 4:
一种木质素增强PE给水管混配料,其包括以下质量份数的组分:树脂100份、改性木质素2.5份、粉体硅烷偶联剂0.5份、增溶剂1份、炭黑0.5份、芳香族二醇类扩链剂0.35份、抗氧化剂1.0份、润滑剂0.18份;所述黑液为高浓度的碱性有机废水,含有大量的有机物和无机盐类物质;所述树脂为PE80;所述粉末硅烷偶联剂为粉末化的3-氨丙基三乙氧基硅烷,且所述粉末化偶联剂是采用硅质惰性吸附剂为载体吸附粉末化的3-氨丙基三乙氧基硅烷而制成的;所述硅质惰性吸附剂为硅酸钙,所述硅酸钙的平均孔径为1.0μm,孔隙率为65%,比表面积为351.15m2/g;所述炭黑的中位粒径D50为18nm,比表面积在750 m2/g;所述增容剂为苯乙烯-甲基丙烯酸环氧丙酯共聚物;所述芳香族二醇类扩链剂为间苯二酚-双(β-羟乙基)醚和氢醌-双(β-羟乙基)醚按照质量比为1:2混合得到的;所述抗氧化剂为受阻酚类抗氧剂和亚磷酸酯抗氧剂按照质量比为1.5:1混合而成;所述润滑剂是数均分子量为2000的聚乙烯蜡;A lignin-reinforced PE water supply pipe mixing material, which includes the following components in parts by mass: 100 parts of resin, 2.5 parts of modified lignin, 0.5 part of powdered silane coupling agent, 1 part of solubilizer, and 0.5 part of carbon black , 0.35 parts of aromatic diol chain extenders, 1.0 parts of antioxidants, and 0.18 parts of lubricants; the black liquor is high-concentration alkaline organic wastewater containing a large amount of organic matter and inorganic salts; the resin is PE80 ; The powdered silane coupling agent is powdered 3-aminopropyltriethoxysilane, and the powdered coupling agent adopts a silicon inert adsorbent as a carrier to absorb powdered 3-aminopropyltriethoxysilane ethoxysilane; the siliceous inert adsorbent is calcium silicate, the average pore diameter of the calcium silicate is 1.0 μm, the porosity is 65%, and the specific surface area is 351.15m 2 /g; The median particle diameter D50 of the carbon black is 18nm, and the specific surface area is 750 m 2 /g; the compatibilizer is styrene-glycidyl methacrylate copolymer; the aromatic diol chain extender is Resorcinol-bis(β-hydroxyethyl) ether and hydroquinone-bis(β-hydroxyethyl) ether are obtained by mixing according to the mass ratio of 1:2; the antioxidant is hindered phenolic antioxidant and The phosphite antioxidant is mixed according to the mass ratio of 1.5:1; the lubricant is a polyethylene wax with a number average molecular weight of 2000;
所述的改性木质素的制备方法包括以下步骤:The preparation method of described modified lignin comprises the following steps:
(1)将碱法制浆得到的黑液浓缩得到固形物含量在28wt%的浓缩液;(1) Concentrating the black liquor obtained by alkaline pulping to obtain a concentrated solution with a solid content of 28wt%;
(2)向步骤(1)中得到的浓缩液中依次加入双氧水和镧铌酸锌,然后在84℃且搅拌速度为300r/min的条件下搅拌反应90min,得到反应液A;所述镧铌酸锌呈片层状,并且所述镧铌酸锌的化学式为Zn1/2LaNb2O7;所述双氧水为30wt%的双氧水;所述浓缩液与双氧水的体积比为1800:3;所述浓缩液的体积与镧铌酸锌的质量比为1800L:200g;(2) Add hydrogen peroxide and zinc lanthanum niobate successively to the concentrated solution obtained in step (1), then stir and react at 84°C and a stirring speed of 300r/min for 90min to obtain reaction solution A; the lanthanum niobium Zinc acid is lamellar, and the chemical formula of zinc lanthanum niobate is Zn 1/2 LaNb 2 O 7 ; the hydrogen peroxide is 30wt% hydrogen peroxide; the volume ratio of the concentrate to hydrogen peroxide is 1800:3; The volume of described concentrate and the mass ratio of zinc lanthanum niobate are 1800L:200g;
(3)将步骤(2)中得到的反应液A冷却至458℃后恒温,接着向反应液A中通入二氧化碳气体,使得反应液A的pH值达到6.5,然后再加入亚磷酸溶液,并且在搅拌速度为300r/min的条件下搅拌反应20min,得到反应液B;所述浓缩液与亚磷酸溶液的体积比为1800:0.25;所述亚磷酸溶液为12wt%的亚磷酸水溶液;(3) Cool the reaction solution A obtained in step (2) to 458°C and then keep the temperature constant, then pass carbon dioxide gas into the reaction solution A, so that the pH value of the reaction solution A reaches 6.5, and then add the phosphorous acid solution, and Stirring and reacting for 20min at a stirring speed of 300r/min to obtain a reaction solution B; the volume ratio of the concentrated solution to the phosphorous acid solution is 1800:0.25; the phosphorous acid solution is a 12wt% phosphorous acid aqueous solution;
(4)将步骤(3)中得到的反应B冷却至室温,接着向反应液B中加入2 wt%的硫酸,使得反应液B的pH值达到2.5,然后再加入阳离子聚丙烯酰胺溶液,得到絮状沉淀物;所述阳离子聚丙烯酰胺溶液为5wt%的阳离子聚丙烯酰胺溶液;所述浓缩液与阳离子聚丙烯酰胺溶液的体积比为1800:0.08;(4) Cool the reaction B obtained in step (3) to room temperature, then add 2 wt% sulfuric acid to the reaction solution B, so that the pH value of the reaction solution B reaches 2.5, and then add the cationic polyacrylamide solution to obtain Flocculent precipitate; the cationic polyacrylamide solution is a 5wt% cationic polyacrylamide solution; the volume ratio of the concentrated solution to the cationic polyacrylamide solution is 1800:0.08;
(5)将步骤(4)中得到的絮状沉淀物压滤得到滤渣,然后将滤渣干燥至含水量小于0.5wt%后得到改性木质素。(5) Press-filter the flocculent precipitate obtained in step (4) to obtain a filter residue, and then dry the filter residue until the water content is less than 0.5wt% to obtain the modified lignin.
本实施例所述木质素增强PE给水管混配料的制备方法,其包括以下步骤:The preparation method of the lignin-enhanced PE water supply pipe mixing material described in this embodiment comprises the following steps:
S1、将改性木质素加入到高速混合机中,以500 r/min的速度搅拌,当温度达到102℃后,加入粉末硅烷偶联剂混合3 min,接着再加入增容剂继续混合8min,然后升温至140℃,再加入芳香族二醇类扩链剂混合5min,接着依次加入炭黑、抗氧化剂、润滑剂及树脂后,搅拌处理12min得到混合物料;S1. Add the modified lignin to the high-speed mixer and stir at a speed of 500 r/min. When the temperature reaches 102°C, add powdered silane coupling agent and mix for 3 minutes, then add compatibilizer and continue mixing for 8 minutes. Then heat up to 140°C, add aromatic diol chain extender and mix for 5 minutes, then add carbon black, antioxidant, lubricant and resin in sequence, and stir for 12 minutes to obtain the mixed material;
S2、将步骤S1中得到的混合物料通过进料口加入到螺杆挤出机中处理后,在通过牵引、冷却切割、筛分后得到木质素增强PE给水管混配料;所述螺杆挤出机中螺杆直径为71mm,螺槽比值为1.5,螺槽深度为14mm,螺杆长径比为40/1,螺杆共分10个加热区,从进料端开始10个加热区的温度依次为135℃、145℃、150℃、155℃、160℃、165℃、170℃、160℃、150℃、140℃;螺杆转速为500rpm。S2. Add the mixed material obtained in step S1 to the screw extruder through the feed port for processing, and obtain lignin-enhanced PE water supply pipe mixed ingredients after traction, cooling, cutting, and screening; the screw extruder The diameter of the middle screw is 71mm, the ratio of the screw groove is 1.5, the depth of the screw groove is 14mm, the ratio of length to diameter of the screw is 40/1, the screw is divided into 10 heating zones, and the temperature of the 10 heating zones starting from the feed end is 135°C , 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, 160°C, 150°C, 140°C; the screw speed is 500rpm.
实施例5:Example 5:
一种木质素增强PE给水管混配料,其包括以下质量份数的组分:树脂100份、改性木质素2份、粉体硅烷偶联剂0.5份、增溶剂0.5份、炭黑0.5份、芳香族二醇类扩链剂0.2份、抗氧化剂0.5份、润滑剂0.05份;所述黑液为高浓度的碱性有机废水,含有大量的有机物和无机盐类物质;所述树脂为PE100;所述粉末硅烷偶联剂为粉末化的3-氨丙基三乙氧基硅烷,且所述粉末化偶联剂是采用硅质惰性吸附剂为载体吸附粉末化的3-氨丙基三乙氧基硅烷而制成的;所述硅质惰性吸附剂为硅酸钙,所述硅酸钙的平均孔径为0.8μm,孔隙率为65%,比表面积为250 m2/g;所述炭黑的中位粒径D50为25 nm,比表面积在500 m2/g;所述增容剂为苯乙烯-甲基丙烯酸环氧丙酯共聚物;所述芳香族二醇类扩链剂为间苯二酚-双(β-羟乙基)醚;所述抗氧化剂为受阻酚类抗氧剂和亚磷酸酯抗氧剂按照质量比为1.5:1混合而成;所述润滑剂是数均分子量为2500的聚乙烯蜡;A lignin-reinforced PE water supply pipe compound, which includes the following components in parts by mass: 100 parts of resin, 2 parts of modified lignin, 0.5 part of powdered silane coupling agent, 0.5 part of solubilizer, and 0.5 part of carbon black , 0.2 parts of aromatic diol chain extenders, 0.5 parts of antioxidants, and 0.05 parts of lubricants; the black liquor is high-concentration alkaline organic wastewater containing a large amount of organic matter and inorganic salts; the resin is PE100 ; The powdered silane coupling agent is powdered 3-aminopropyltriethoxysilane, and the powdered coupling agent adopts a silicon inert adsorbent as a carrier to absorb powdered 3-aminopropyltriethoxysilane ethoxysilane; the siliceous inert adsorbent is calcium silicate, the average pore diameter of the calcium silicate is 0.8 μm, the porosity is 65%, and the specific surface area is 250 m 2 /g; The median particle size D50 of carbon black is 25 nm, and the specific surface area is 500 m 2 /g; the compatibilizer is styrene-glycidyl methacrylate copolymer; the aromatic diol chain extender It is resorcinol-bis(β-hydroxyethyl) ether; the antioxidant is a mixture of hindered phenolic antioxidant and phosphite antioxidant according to the mass ratio of 1.5:1; the lubricant is Polyethylene wax with a number average molecular weight of 2500;
所述的改性木质素的制备方法包括以下步骤:The preparation method of described modified lignin comprises the following steps:
(1)将碱法制浆得到的黑液浓缩得到固形物含量在20wt%的浓缩液;(1) Concentrating the black liquor obtained by alkaline pulping to obtain a concentrated solution with a solid content of 20wt%;
(2)向步骤(1)中得到的浓缩液中依次加入双氧水和镧铌酸锌,然后在80℃且搅拌速度为300r/min的条件下搅拌反应90min,得到反应液A;所述镧铌酸锌呈片层状,并且所述镧铌酸锌的化学式为Zn1/2LaNb2O7;所述双氧水为30wt%的双氧水;所述浓缩液与双氧水的体积比为80:1;所述浓缩液的体积与镧铌酸锌的质量比为5L:1g;(2) Add hydrogen peroxide and zinc lanthanum niobate successively to the concentrated solution obtained in step (1), then stir and react at 80°C and a stirring speed of 300r/min for 90min to obtain reaction solution A; the lanthanum niobium Zinc acid is lamellar, and the chemical formula of zinc lanthanum niobate is Zn 1/2 LaNb 2 O 7 ; the hydrogen peroxide is 30wt% hydrogen peroxide; the volume ratio of the concentrated solution to hydrogen peroxide is 80:1; The volume of said concentrate and the mass ratio of zinc lanthanum niobate are 5L:1g;
(3)将步骤(2)中得到的反应液A冷却至45℃后恒温,接着向反应液A中通入二氧化碳气体,使得反应液A的pH值达到6.0,然后再加入亚磷酸溶液,并且在搅拌速度为300r/min的条件下搅拌反应20min,得到反应液B;所述浓缩液与亚磷酸溶液的体积比为500:0.1;所述亚磷酸溶液为10wt%的亚磷酸水溶液;(3) Cool the reaction solution A obtained in step (2) to 45°C and keep the temperature, then pass carbon dioxide gas into the reaction solution A, so that the pH value of the reaction solution A reaches 6.0, and then add the phosphorous acid solution, and Stirring and reacting for 20min at a stirring speed of 300r/min to obtain a reaction solution B; the volume ratio of the concentrated solution to the phosphorous acid solution is 500:0.1; the phosphorous acid solution is a 10wt% phosphorous acid aqueous solution;
(4)将步骤(3)中得到的反应B冷却至室温,接着向反应液B中加入2 wt%的硫酸,使得反应液B的pH值达到2.0,然后再加入阳离子聚丙烯酰胺溶液,得到絮状沉淀物;所述阳离子聚丙烯酰胺溶液为5wt%的阳离子聚丙烯酰胺溶液;所述浓缩液与阳离子聚丙烯酰胺溶液的体积比为1000:0.1;(4) Cool the reaction B obtained in step (3) to room temperature, then add 2 wt% sulfuric acid to the reaction solution B, so that the pH value of the reaction solution B reaches 2.0, and then add the cationic polyacrylamide solution to obtain Flocculent precipitate; the cationic polyacrylamide solution is a 5wt% cationic polyacrylamide solution; the volume ratio of the concentrated solution to the cationic polyacrylamide solution is 1000:0.1;
(5)将步骤(4)中得到的絮状沉淀物压滤得到滤渣,然后将滤渣干燥至含水量小于0.5wt%后得到改性木质素。(5) Press-filter the flocculent precipitate obtained in step (4) to obtain a filter residue, and then dry the filter residue until the water content is less than 0.5wt% to obtain the modified lignin.
本实施例所述木质素增强PE给水管混配料的制备方法,其包括以下步骤:The preparation method of the lignin-enhanced PE water supply pipe mixing material described in this embodiment comprises the following steps:
S1、将改性木质素加入到高速混合机中,以500 r/min的速度搅拌,当温度达到80℃后,加入粉末硅烷偶联剂混合3 min,接着再加入增容剂继续混合5min,然后升温至140℃,再加入芳香族二醇类扩链剂混合5min,接着依次加入炭黑、抗氧化剂、润滑剂及树脂后,搅拌处理10min得到混合物料;S1. Add the modified lignin to the high-speed mixer and stir at a speed of 500 r/min. When the temperature reaches 80°C, add powdered silane coupling agent and mix for 3 minutes, then add compatibilizer and continue mixing for 5 minutes. Then heat up to 140°C, add aromatic diol chain extender and mix for 5 minutes, then add carbon black, antioxidant, lubricant and resin in sequence, and stir for 10 minutes to obtain the mixed material;
S2、将步骤S1中得到的混合物料通过进料口加入到螺杆挤出机中处理后,在通过牵引、冷却切割、筛分后得到木质素增强PE给水管混配料;所述螺杆挤出机中螺杆直径为71mm,螺槽比值为1.5,螺槽深度为14mm,螺杆长径比为40/1,螺杆共分10个加热区,从进料端开始10个加热区的温度依次为135℃、145℃、150℃、155℃、160℃、165℃、170℃、160℃、150℃、140℃;螺杆转速为500rpm。S2. Add the mixed material obtained in step S1 to the screw extruder through the feed port for processing, and obtain lignin-enhanced PE water supply pipe mixed ingredients after traction, cooling, cutting, and screening; the screw extruder The diameter of the middle screw is 71mm, the ratio of the screw groove is 1.5, the depth of the screw groove is 14mm, the ratio of length to diameter of the screw is 40/1, the screw is divided into 10 heating zones, and the temperature of the 10 heating zones starting from the feed end is 135°C , 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, 160°C, 150°C, 140°C; the screw speed is 500rpm.
实施例6:Embodiment 6:
一种木质素增强PE给水管混配料,其包括以下质量份数的组分:树脂100份、改性木质素3份、粉体硅烷偶联剂0.5份、增溶剂1.5份、炭黑1.5份、芳香族二醇类扩链剂1份、抗氧化剂1.5份、润滑剂0.2份;所述黑液为高浓度的碱性有机废水,含有大量的有机物和无机盐类物质;所述树脂为PE80;所述粉末硅烷偶联剂为粉末化的3-氨丙基三乙氧基硅烷,且所述粉末化偶联剂是采用硅质惰性吸附剂为载体吸附粉末化的3-氨丙基三乙氧基硅烷而制成的;所述硅质惰性吸附剂为硅酸钙,所述硅酸钙的平均孔径为1.2μm,孔隙率为80%,比表面积为400 m2/g;所述炭黑的中位粒径D50为10 nm,比表面积在500 m2/g;所述增容剂为苯乙烯-甲基丙烯酸环氧丙酯共聚物;所述芳香族二醇类扩链剂为氢醌-双(β-羟乙基)醚;所述抗氧化剂为受阻酚类抗氧剂和亚磷酸酯抗氧剂按照质量比为1.5:1混合而成;所述润滑剂是数均分子量为2500的聚乙烯蜡;A lignin-reinforced PE water supply pipe compounding material, which includes the following components in parts by mass: 100 parts of resin, 3 parts of modified lignin, 0.5 parts of powdered silane coupling agent, 1.5 parts of solubilizer, and 1.5 parts of carbon black , 1 part of aromatic diol chain extender, 1.5 parts of antioxidant, 0.2 part of lubricant; the black liquor is alkaline organic wastewater with high concentration, containing a large amount of organic matter and inorganic salts; the resin is PE80 ; The powdered silane coupling agent is powdered 3-aminopropyltriethoxysilane, and the powdered coupling agent adopts a silicon inert adsorbent as a carrier to absorb powdered 3-aminopropyltriethoxysilane ethoxysilane; the siliceous inert adsorbent is calcium silicate, the average pore diameter of the calcium silicate is 1.2 μm, the porosity is 80%, and the specific surface area is 400 m 2 /g; The median particle diameter D50 of carbon black is 10 nm, and the specific surface area is 500 m 2 /g; the compatibilizer is styrene-glycidyl methacrylate copolymer; the aromatic diol chain extender It is hydroquinone-bis(β-hydroxyethyl) ether; the antioxidant is a mixture of hindered phenolic antioxidant and phosphite antioxidant according to the mass ratio of 1.5:1; the lubricant is a number average Polyethylene wax with a molecular weight of 2500;
所述的改性木质素的制备方法包括以下步骤:The preparation method of described modified lignin comprises the following steps:
(1)将碱法制浆得到的黑液浓缩得到固形物含量在35wt%的浓缩液;(1) Concentrating the black liquor obtained by alkaline pulping to obtain a concentrated solution with a solid content of 35wt%;
(2)向步骤(1)中得到的浓缩液中依次加入双氧水和镧铌酸锌,然后在85℃且搅拌速度为300r/min的条件下搅拌反应90min,得到反应液A;所述镧铌酸锌呈片层状,并且所述镧铌酸锌的化学式为ZnLa2/3Nb2O7;所述双氧水为30wt%的双氧水;所述浓缩液与双氧水的体积比为800:1;所述浓缩液的体积与镧铌酸锌的质量比为25L:1g;(2) Add hydrogen peroxide and zinc lanthanum niobate sequentially to the concentrated solution obtained in step (1), then stir and react at 85°C and a stirring speed of 300r/min for 90min to obtain reaction solution A; the lanthanum niobium Zinc acid is lamellar, and the chemical formula of zinc lanthanum niobate is ZnLa 2/3 Nb 2 O 7 ; the hydrogen peroxide is 30wt% hydrogen peroxide; the volume ratio of the concentrate to hydrogen peroxide is 800:1; The volume of said concentrate and the mass ratio of zinc lanthanum niobate are 25L:1g;
(3)将步骤(2)中得到的反应液A冷却至45℃~50℃后恒温,接着向反应液A中通入二氧化碳气体,使得反应液A的pH值达到6.0~6.5,然后再加入亚磷酸溶液,并且在搅拌速度为300r/min的条件下搅拌反应20min,得到反应液B;所述浓缩液与亚磷酸溶液的体积比为3000:0.1;所述亚磷酸溶液为25wt%的亚磷酸水溶液;(3) Cool the reaction solution A obtained in step (2) to 45°C-50°C and keep the temperature constant, then pass carbon dioxide gas into the reaction solution A so that the pH value of the reaction solution A reaches 6.0-6.5, and then add Phosphorous acid solution, and stirring reaction 20min under the condition of 300r/min at stirring speed, obtains reaction solution B; The volume ratio of described concentrated solution and phosphorous acid solution is 3000:0.1; Described phosphorous acid solution is the phosphorous acid solution of 25wt%. Phosphoric acid aqueous solution;
(4)将步骤(3)中得到的反应B冷却至室温,接着向反应液B中加入2 wt%的硫酸,使得反应液B的pH值达到3.0,然后再加入阳离子聚丙烯酰胺溶液,得到絮状沉淀物;所述阳离子聚丙烯酰胺溶液为5wt%的阳离子聚丙烯酰胺溶液;所述浓缩液与阳离子聚丙烯酰胺溶液的体积比为2500:0.1;(4) Cool the reaction B obtained in step (3) to room temperature, then add 2 wt% sulfuric acid to the reaction solution B, so that the pH value of the reaction solution B reaches 3.0, and then add the cationic polyacrylamide solution to obtain Flocculent precipitate; the cationic polyacrylamide solution is 5wt% cationic polyacrylamide solution; the volume ratio of the concentrated solution to the cationic polyacrylamide solution is 2500:0.1;
(5)将步骤(4)中得到的絮状沉淀物压滤得到滤渣,然后将滤渣干燥至含水量小于0.5wt%后得到改性木质素。(5) Press-filter the flocculent precipitate obtained in step (4) to obtain a filter residue, and then dry the filter residue until the water content is less than 0.5wt% to obtain the modified lignin.
本实施例所述木质素增强PE给水管混配料的制备方法,其包括以下步骤:The preparation method of the lignin-enhanced PE water supply pipe mixing material described in this embodiment comprises the following steps:
S1、将改性木质素加入到高速混合机中,以500 r/min的速度搅拌,当温度达到110℃后,加入粉末硅烷偶联剂混合3 min,接着再加入增容剂继续混合10min,然后升温至140℃,再加入芳香族二醇类扩链剂混合5min,接着依次加入炭黑、抗氧化剂、润滑剂及树脂后,搅拌处理12min得到混合物料;S1. Add the modified lignin to the high-speed mixer and stir at a speed of 500 r/min. When the temperature reaches 110°C, add powdered silane coupling agent and mix for 3 minutes, then add compatibilizer and continue mixing for 10 minutes. Then heat up to 140°C, add aromatic diol chain extender and mix for 5 minutes, then add carbon black, antioxidant, lubricant and resin in sequence, and stir for 12 minutes to obtain the mixed material;
S2、将步骤S1中得到的混合物料通过进料口加入到螺杆挤出机中处理后,在通过牵引、冷却切割、筛分后得到木质素增强PE给水管混配料;所述螺杆挤出机中螺杆直径为71mm,螺槽比值为1.5,螺槽深度为14mm,螺杆长径比为40/1,螺杆共分10个加热区,从进料端开始10个加热区的温度依次为135℃、145℃、150℃、155℃、160℃、165℃、170℃、160℃、150℃、140℃;螺杆转速为500rpm。S2. Add the mixed material obtained in step S1 to the screw extruder through the feed port for processing, and obtain lignin-enhanced PE water supply pipe mixed ingredients after traction, cooling, cutting, and screening; the screw extruder The diameter of the middle screw is 71mm, the ratio of the screw groove is 1.5, the depth of the screw groove is 14mm, the ratio of length to diameter of the screw is 40/1, the screw is divided into 10 heating zones, and the temperature of the 10 heating zones starting from the feed end is 135°C , 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, 160°C, 150°C, 140°C; the screw speed is 500rpm.
对比例1:Comparative example 1:
本对比例与实施例1所述木质素增强PE给水管混配料的区别仅在于,将原木质素替换成改性木质素使用,所述原木质素的制备方法是将碱法制浆黑液浓缩至固形物含量在30 wt%的浓缩液,接着取1000L浓缩液,在搅拌条件下加入72 wt%的H2SO4溶液,使溶液pH达到2~3即可形成大量絮状沉淀,充分静置后,通过板框压滤实现固液分离,所得到的固体用大量去离子水冲洗至洗液呈中性后,在60℃下真空干燥至含水量小于0.5wt%,即得原木质素;所述木质素增强PE给水管混配料的制备方法与实施例1中所述方法一致。The difference between this comparative example and the lignin-enhanced PE water supply pipe mixing material described in Example 1 is that the original lignin is replaced with modified lignin, and the original lignin is prepared by making alkaline pulping black liquor Concentrate to a concentrated solution with a solid content of 30 wt%, then take 1000L of the concentrated solution, add 72 wt% H2SO4 solution under stirring conditions, and make the pH of the solution reach 2~3 to form a large number of flocculent precipitates, fully After standing still, the solid-liquid separation is realized by plate and frame filtration, and the obtained solid is washed with a large amount of deionized water until the washing liquid is neutral, and then vacuum-dried at 60°C until the water content is less than 0.5wt%, that is, the log The preparation method of the lignin-enhanced PE water supply pipe compound is consistent with the method described in Example 1.
对比例2:Comparative example 2:
本对比例与实施例1所述木质素增强PE给水管混配料的区别仅在于,不使用所述的粉体硅烷偶联剂,其他步骤与实施例1中所述方法一致。The difference between this comparative example and the lignin-reinforced PE water supply pipe compound described in Example 1 is that the powder silane coupling agent is not used, and the other steps are consistent with the method described in Example 1.
对比例3:Comparative example 3:
本对比例与实施例1所述木质素增强PE给水管混配料的区别仅在于,所述粉体硅烷偶联剂仅为粉末化的3-氨丙基三乙氧基硅烷,未使用硅酸钙进行吸附,其他步骤与实施例1中所述方法一致。The only difference between this comparative example and the lignin-enhanced PE water supply pipe mixture described in Example 1 is that the powdered silane coupling agent is only powdered 3-aminopropyltriethoxysilane, and no silicic acid is used. Calcium is adsorbed, and other steps are consistent with the method described in Example 1.
对比例4:Comparative example 4:
本对比例与实施例1所述木质素增强PE给水管混配料的区别仅在于,不使用所述的增溶剂,其他步骤与实施例1中所述方法一致。The difference between this comparative example and the lignin-reinforced PE water supply pipe compound described in Example 1 is that the solubilizer is not used, and the other steps are consistent with the method described in Example 1.
对比例5:Comparative example 5:
本对比例与实施例1所述木质素增强PE给水管混配料的区别仅在于,所述增溶剂为PE-g-MAH,其他步骤与实施例1中所述方法一致。The difference between this comparative example and the lignin-reinforced PE water supply pipe mixture described in Example 1 is that the solubilizer is PE-g-MAH, and the other steps are consistent with the method described in Example 1.
对比例6:Comparative example 6:
本对比例与实施例1所述木质素增强PE给水管混配料的区别仅在于,不使用所述的扩链剂,其他步骤与实施例1中所述方法一致。The difference between this comparative example and the lignin-reinforced PE water supply pipe compound described in Example 1 is that the chain extender is not used, and the other steps are consistent with the method described in Example 1.
对比例7:Comparative example 7:
本对比例与实施例1所述木质素增强PE给水管混配料的区别仅在于,所述扩链剂为Joncryl ADR 4370F,其他步骤与实施例1中所述方法一致。The difference between this comparative example and the lignin-reinforced PE water supply pipe compound described in Example 1 is that the chain extender is Joncryl ADR 4370F, and the other steps are the same as those described in Example 1.
对比例8:Comparative example 8:
本对比例与实施例1所述木质素增强PE给水管混配料的区别仅在于,在制备改性木质素时,未添加镧铌酸锌,其他步骤与实施例1中所述方法一致。The difference between this comparative example and the lignin-reinforced PE water supply pipe compound described in Example 1 is that no zinc lanthanum niobate was added when preparing the modified lignin, and the other steps were consistent with the method described in Example 1.
对比例9:Comparative example 9:
本对比例与实施例1所述木质素增强PE给水管混配料的区别仅在于,不加入改性木质素,其他步骤与实施例1中所述方法一致。The difference between this comparative example and the lignin-reinforced PE water supply pipe mixture described in Example 1 is that no modified lignin is added, and the other steps are consistent with the method described in Example 1.
实验例:Experimental example:
按照实施例1~6以及对比例1~9所述方法制备改性木质素和混配料,然后按照以下方法进行检测,检测结果参见表1和表2。The modified lignin and the mixed ingredients were prepared according to the methods described in Examples 1-6 and Comparative Examples 1-9, and then tested according to the following method. See Table 1 and Table 2 for the test results.
(1)木质素结构测定:(1) Determination of lignin structure:
木质素的酚羟基含量根据以下文献内容进行测定:吴保国,赵菊兰,杜晶滨.差示紫外光谱法测定木素酚羟基含量[J]. 东北林业大学学报,1993,02(21),58~65 。 The phenolic hydroxyl content of lignin was determined according to the following literature: Wu Baoguo, Zhao Julan, Du Jingbin. Determination of lignin phenolic hydroxyl content by differential ultraviolet spectroscopy [J]. Journal of Northeast Forestry University, 1993, 02 (21), 58~65.
木质素的分子量和分子量分布采用Waters 1515/2414凝胶渗透色谱仪测定,测试柱温保持40℃,1 ml/min的流速,以三根Waters的色谱柱串联(Styragel HR1、HR3和HR4),DMF作流动相,德国PSS的聚苯乙烯为标样(Mp= 246000,184000,120000,44200,18200, 9890, 6520, 2770, 890, 474, 370,PDI<1.20)。 The molecular weight and molecular weight distribution of lignin were measured by Waters 1515/2414 gel permeation chromatography, the test column temperature was kept at 40°C, the flow rate was 1 ml/min, three Waters chromatographic columns were connected in series (Styragel HR1, HR3 and HR4), DMF As the mobile phase, the polystyrene of PSS in Germany was used as the standard sample (Mp= 246000, 184000, 120000, 44200, 18200, 9890, 6520, 2770, 890, 474, 370, PDI<1.20).
木质素的玻璃化转变温度采用TA 公司的Q20差示扫描量热法测定,测试在N2氛围中,以10 ℃/min的升温速度进行。 The glass transition temperature of lignin was measured by Q20 differential scanning calorimetry of TA Company, and the test was carried out in N 2 atmosphere at a heating rate of 10 ℃/min.
1H-NMR测试是将2~3 mg BL溶于10 ml DMSO-d6后取清澈的上层溶液,通过美国Agilent 800MHz核磁共振波谱仪进行。 1H-NMR test is to dissolve 2~3 mg BL in 10 ml DMSO-d6 and take the clear upper layer solution, which is carried out by American Agilent 800MHz nuclear magnetic resonance spectrometer.
(2)混配料的性能测定:将所得混配料通过注塑机在170℃、45MPa条件下注塑制成哑铃型标准拉伸测试样条。通过电子万能试验机测试拉伸强度及断裂伸长率,通过悬臂梁冲击试验仪测试冲击强度。测试条件:拉伸强度、断裂伸长率参照标准GB/T 1040.2-2006测试;冲击强度按标准GB/T 1043.1-2008测试;将所得混配料通过管道挤出机制成规格为DN110, SDR17的PE给水管,根据国标GB/T13663-2018测定产品的静液压强度、氧化诱导时间和纵向回缩率。(2) Performance measurement of the mixed ingredients: the obtained mixed ingredients were injection molded by an injection molding machine under the conditions of 170° C. and 45 MPa to make dumbbell-shaped standard tensile test specimens. The tensile strength and elongation at break were tested by an electronic universal testing machine, and the impact strength was tested by a cantilever beam impact tester. Test conditions: Tensile strength and elongation at break are tested according to the standard GB/T 1040.2-2006; impact strength is tested according to the standard GB/T 1043.1-2008; the obtained compound is made into PE with specifications of DN110 and SDR17 through a pipeline extruder For the water supply pipe, the hydrostatic strength, oxidation induction time and longitudinal retraction rate of the product are measured according to the national standard GB/T13663-2018.
表1 不同方法制备得到的木质素测定结果Table 1 Determination results of lignin prepared by different methods
表2 不同方法制备得到的大口径聚乙烯给水管性能检测结果Table 2 Performance test results of large-diameter polyethylene water supply pipes prepared by different methods
从表1可以看出,对比例1中1000L固形物含量为30wt%的造纸黑液回收得到的木质素为188.60 Kg,其酚羟基含量为的收率为2.45 mmol/g;而实施例1~6中1000L固形物含量为30wt%的造纸黑液回收得到的木质素为190 Kg以上,其酚羟基含量为2.5 mmol/g以上。说明经本发明低温氧化-亚磷酸还原-酸析絮凝处理后,可以有效增加木质素分子链段中的活性羟基数量,进而更易于与硅烷偶联剂、相容剂和扩链剂发生反应。同时,造纸黑液中的木质素由酸溶木质素和酸不溶木质素构成,本发明与对比例1相比,获得了更高的木质素收率,说明经本发明低温氧化-亚磷酸还原-酸析絮凝处理后,可以促进部分酸溶性木质素转变为酸不溶性木质素,进而形成沉淀析出。As can be seen from Table 1, in comparative example 1, the lignin that the papermaking black liquor that 1000L solid content is 30wt% reclaims is 188.60 Kg, and the yield of its phenolic hydroxyl content is 2.45 mmol/g; And embodiment 1~ The lignin recovered from 1000L papermaking black liquor with a solid content of 30wt% in 6 is more than 190 Kg, and its phenolic hydroxyl content is more than 2.5 mmol/g. It shows that after the low-temperature oxidation-phosphorous acid reduction-acid flocculation treatment of the present invention, the number of active hydroxyl groups in the lignin molecular chain segment can be effectively increased, and then it is easier to react with the silane coupling agent, compatibilizer and chain extender. Simultaneously, the lignin in the papermaking black liquor is composed of acid-soluble lignin and acid-insoluble lignin. Compared with Comparative Example 1, the present invention obtains a higher yield of lignin, indicating that the low-temperature oxidation-phosphorous acid reduction of the present invention - After acid flocculation treatment, it can promote the transformation of part of acid-soluble lignin into acid-insoluble lignin, and then form precipitation.
从表2可以看出,在实施例1的物料配比上,无论是去掉增容剂或扩链剂或镧铌酸锌催化剂,还是以常规的PE-g-MAH增容剂替换本发明所要求的苯乙烯-甲基丙烯酸环氧丙酯共聚物(PS-co -GMA)增容剂,或以常规的Joncryl ADR 4370F扩链剂替换本发明技术所要求的间苯二酚-双(β-羟乙基)醚/氢醌-双(β-羟乙基)醚混合型扩链剂,所得木质素-PE复合材料的拉伸强度、断裂伸长率及冲击强度等力学性能指标都有了不同程度的削减,说明经本发明技术获得的改性木质素,与本发明技术所要求的增容剂、扩链剂之间可以起到协同作用,从而获得了更优的综合性能。As can be seen from Table 2, on the proportioning of materials in Example 1, whether it is to remove the compatibilizer or chain extender or zinc lanthanum niobate catalyst, or replace the present invention with conventional PE-g-MAH compatibilizer The required styrene-glycidyl methacrylate copolymer (PS-co-GMA) compatibilizer, or replace the resorcinol-bis(β -Hydroxyethyl) ether/hydroquinone-bis(β-hydroxyethyl)ether mixed chain extender, the obtained lignin-PE composites have mechanical properties such as tensile strength, elongation at break and impact strength. It shows that the modified lignin obtained by the technology of the present invention can play a synergistic effect with the compatibilizer and chain extender required by the technology of the present invention, thereby obtaining better comprehensive performance.
同时,从图1可以看出,通过本发明低温氧化-亚磷酸还原-酸析絮凝处理后,原木质素颗粒崩裂成为许多大小不一的细小颗粒,颗粒大小约1.0~2μm。At the same time, it can be seen from Figure 1 that after the low-temperature oxidation-phosphorous acid reduction-acid flocculation treatment of the present invention, the original lignin particles are disintegrated into many fine particles of different sizes, and the particle size is about 1.0-2 μm.
从图2可以看出,原木质素(对比例1)的GPC谱图并不是单一的峰,而是表现为连续分布的双重峰,分别为数均分子量107106 g/mol,分子量分布(PDI=2.159)以及数均分子量11270g/mol,分子量分布(PDI=1.371)分布峰,说明原木质素(对比例1)的分子量分布较宽,分子之间存在较大差异。通过本发明低温氧化-亚磷酸还原-酸析絮凝处理后,所得改性木质素的GPC谱图呈现为单一的分布峰,数均分子量和分子量分布分别为4897 g/mol和1.360,说明本发明技术处理可以有效降低木质素分子量,形成更多的小分子木质素链段。It can be seen from Figure 2 that the GPC spectrum of the original lignin (Comparative Example 1) is not a single peak, but a continuous distribution of double peaks, respectively, the number average molecular weight is 107106 g/mol, and the molecular weight distribution (PDI=2.159 ) and the number average molecular weight of 11270g/mol, and the distribution peak of the molecular weight distribution (PDI=1.371), indicating that the molecular weight distribution of the original lignin (Comparative Example 1) is relatively wide, and there are large differences between molecules. After the low-temperature oxidation-phosphorous acid reduction-acid flocculation treatment of the present invention, the GPC spectrogram of the obtained modified lignin presents a single distribution peak, and the number average molecular weight and molecular weight distribution are 4897 g/mol and 1.360 respectively, illustrating the present invention Technical treatment can effectively reduce the molecular weight of lignin and form more small molecular lignin segments.
由于,木质素是无定形的热塑性高聚物,没有熔点,但具有玻璃态转化性质,在一定的压力下,会发生软化并具有流动性和有胶黏性,因此木质素的玻璃化转变温度(Tg)是影响木质素-PE加工性能的关键因素。从图3可以看出,原木质素(对比例1)的玻璃化转变温度为138.1℃,通过本发明低温氧化-亚磷酸还原-酸析絮凝处理后,所得改性木质素的玻璃化转变温度为下降为128.3℃,说明本发明技术处理可以有效降低木质素的玻璃化转变温度,可增加复合材料在更低温度条件下的流动性,有利于复合材料的加工成型。Since lignin is an amorphous thermoplastic polymer, it has no melting point, but has a glass transition property. Under a certain pressure, it will soften and have fluidity and adhesiveness, so the glass transition temperature of lignin (Tg) is a key factor affecting the processing performance of lignin-PE. It can be seen from Figure 3 that the glass transition temperature of the original lignin (Comparative Example 1) is 138.1°C. The lower temperature is 128.3°C, which shows that the technical treatment of the present invention can effectively reduce the glass transition temperature of lignin, increase the fluidity of composite materials at lower temperatures, and facilitate the processing and molding of composite materials.
从图4和图5可以看出,对比例1(图5)中,木质素呈坚硬的颗粒状,并存在团聚现象,其与PE基体树脂间存在界面差异,彼此间的间隙明显,说明原木质素与PE树脂间的相容性较差,单纯通过熔融挤出难以获取界面连续、均匀的复合材料。而实施例1(图4)所得的木质素-PE复合材料中,木质素与PE基体树脂间已几乎容为一体,彼此间观察不到明显的缝隙或孔洞,说明通过本发明技术处理,可以有效提升木质素与PE树脂的相容性。It can be seen from Figure 4 and Figure 5 that in Comparative Example 1 (Figure 5), the lignin was hard granular and agglomerated, and there was an interface difference between it and the PE matrix resin, and the gap between them was obvious, indicating that the log The compatibility between quality and PE resin is poor, and it is difficult to obtain a continuous and uniform composite material through melt extrusion alone. However, in the lignin-PE composite material obtained in Example 1 (Figure 4), the lignin and the PE matrix resin are almost integrated, and no obvious gaps or holes can be observed between each other, which shows that the technology of the present invention can be processed. Effectively improve the compatibility of lignin and PE resin.
从图6可以看出,PE的拉伸强度和断裂伸长率分别为24.35 MPa和1736.27%;而直接采用原木质素(对比例1)进行共混制备的复合材料的拉伸强度和断裂伸长率分别为14.39MPa和588.38%,说明原木质素与PE直接共混所得复合材料存在相缺陷,在受力时容易成为断裂点,进而降低复合材料力学性能。通过实施例1所得的木质素-PE复合材料,其拉伸强度和断裂伸长率分别为32.49 MPa和1834.36%,较PE有了较大提升,说明本发明技术所得复合材料,可以有效增加PE的拉伸强度、断裂伸长率等综合性能。It can be seen from Figure 6 that the tensile strength and elongation at break of PE are 24.35 MPa and 1736.27% respectively; while the tensile strength and elongation at break of the composite material directly blended with raw lignin (Comparative Example 1) The elongation ratios are 14.39MPa and 588.38%, respectively, indicating that the composite material obtained by direct blending of raw lignin and PE has phase defects, which tend to become fracture points when stressed, thereby reducing the mechanical properties of the composite material. The tensile strength and elongation at break of the lignin-PE composite material obtained in Example 1 are 32.49 MPa and 1834.36%, respectively, which are greatly improved compared with PE, indicating that the composite material obtained by the technology of the present invention can effectively increase PE. Comprehensive properties such as tensile strength and elongation at break.
此外,应当理解,虽然本说明书按照实施方式加以描述,但并非每个实施方式仅包含一个独立的技术方案,说明书的这种叙述方式仅仅是为清楚起见,本领域技术人员应当将说明书作为一个整体,各实施例中的技术方案也可以经适当组合,形成本领域技术人员可以理解的其他实施方式。In addition, it should be understood that although this specification is described according to implementation modes, not each implementation mode only contains an independent technical solution, and this description in the specification is only for clarity, and those skilled in the art should take the specification as a whole , the technical solutions in the various embodiments can also be properly combined to form other implementations that can be understood by those skilled in the art.
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