WO2011140706A1 - Hemp fiber for plastic reinforcement and preparation method thereof - Google Patents
Hemp fiber for plastic reinforcement and preparation method thereof Download PDFInfo
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- WO2011140706A1 WO2011140706A1 PCT/CN2010/072652 CN2010072652W WO2011140706A1 WO 2011140706 A1 WO2011140706 A1 WO 2011140706A1 CN 2010072652 W CN2010072652 W CN 2010072652W WO 2011140706 A1 WO2011140706 A1 WO 2011140706A1
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- WIPO (PCT)
- Prior art keywords
- hemp fiber
- fiber
- parts
- coupling agent
- hemp
- Prior art date
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- 239000000835 fiber Substances 0.000 title claims abstract description 160
- 244000025254 Cannabis sativa Species 0.000 title claims abstract description 127
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 title claims abstract description 127
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 title claims abstract description 127
- 235000009120 camo Nutrition 0.000 title claims abstract description 127
- 235000005607 chanvre indien Nutrition 0.000 title claims abstract description 127
- 239000011487 hemp Substances 0.000 title claims abstract description 127
- 239000004033 plastic Substances 0.000 title claims abstract description 45
- 229920003023 plastic Polymers 0.000 title claims abstract description 45
- 230000002787 reinforcement Effects 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- 239000007822 coupling agent Substances 0.000 claims abstract description 32
- 229920000098 polyolefin Polymers 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 239000007864 aqueous solution Substances 0.000 claims abstract description 19
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 15
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000004640 Melamine resin Substances 0.000 claims description 11
- 229920000877 Melamine resin Polymers 0.000 claims description 11
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 7
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 7
- 239000012948 isocyanate Substances 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 6
- -1 polypropylene Polymers 0.000 claims description 6
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 5
- USDJGQLNFPZEON-UHFFFAOYSA-N [[4,6-bis(hydroxymethylamino)-1,3,5-triazin-2-yl]amino]methanol Chemical compound OCNC1=NC(NCO)=NC(NCO)=N1 USDJGQLNFPZEON-UHFFFAOYSA-N 0.000 claims description 5
- YGCOKJWKWLYHTG-UHFFFAOYSA-N [[4,6-bis[bis(hydroxymethyl)amino]-1,3,5-triazin-2-yl]-(hydroxymethyl)amino]methanol Chemical compound OCN(CO)C1=NC(N(CO)CO)=NC(N(CO)CO)=N1 YGCOKJWKWLYHTG-UHFFFAOYSA-N 0.000 claims description 5
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical group OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 240000008564 Boehmeria nivea Species 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 150000004645 aluminates Chemical class 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 150000002910 rare earth metals Chemical class 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 244000198134 Agave sisalana Species 0.000 claims description 3
- 240000000491 Corchorus aestuans Species 0.000 claims description 3
- 235000011777 Corchorus aestuans Nutrition 0.000 claims description 3
- 235000010862 Corchorus capsularis Nutrition 0.000 claims description 3
- 240000006240 Linum usitatissimum Species 0.000 claims description 3
- 235000004431 Linum usitatissimum Nutrition 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 239000011733 molybdenum Substances 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 8
- 238000004898 kneading Methods 0.000 abstract description 8
- 239000011159 matrix material Substances 0.000 abstract description 3
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 241000196324 Embryophyta Species 0.000 description 12
- 230000003014 reinforcing effect Effects 0.000 description 9
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- 229920001587 Wood-plastic composite Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000011151 fibre-reinforced plastic Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011155 wood-plastic composite Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002557 mineral fiber Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- WTHDKMILWLGDKL-UHFFFAOYSA-N urea;hydrate Chemical compound O.NC(N)=O WTHDKMILWLGDKL-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
- B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/01—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with hydrogen, water or heavy water; with hydrides of metals or complexes thereof; with boranes, diboranes, silanes, disilanes, phosphines, diphosphines, stibines, distibines, arsines, or diarsines or complexes thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
Definitions
- the invention belongs to the technical field of natural fiber composite materials and wood plastic composite materials, and particularly relates to a plastic reinforcing hemp fiber and a preparation method thereof
- Natural plant fibers are formed by long-fiber or braided fiber mats and then thermoformed with thermosetting resins. They cannot be directly added to thermoplastics for injection molding like glass fibers.
- natural plant fibers are rich in hydroxyl groups on the one hand. , showing strong polarity and hydrophilicity, poor compatibility with non-polar or weakly polar plastics, poor performance of prepared composites; on the other hand, due to the large volume of plant fibers, large filling capacity, fibers and The large friction between plastics, fibers and equipment and fibers makes plant fiber reinforced plastics difficult to process, especially for injection molding.
- interface compatibilizer In order to solve the problem of compatibility between plant fiber and plastic interface, the main solution at present is to add interface compatibilizer, one type is coupling agent, such as silane coupling agent, titanate coupling agent, aluminate coupling. Agent, rare earth coupling agent, The isocyanate coupling agent and the like, and the other is a graft or copolymer of maleic anhydride and a polyolefin. Most of the coupling agents are used in small amounts of liquid and are not easily dispersed uniformly in plant fibers, affecting the coupling effect. Industrial applications require special equipment to handle; grafts or copolymers of maleic anhydride and polyolefin are mostly particles.
- Another object of the present invention is to provide a method for producing the above-mentioned plastic reinforcing hemp fiber.
- a hemp fiber for plastic reinforcement consists of the following components by weight:
- Hemp fiber treatment agent 0.1 to 100 parts (preferably 10 to 80 parts)
- the short cut hemp fiber is one or more of ramie fiber, flax fiber, sisal fiber, jute fiber, and hemp fiber.
- the hemp fiber treating agent is a urea-formaldehyde resin prepolymer, a trimethylol melamine resin or a hexamethylol melamine resin.
- the functional polyolefin is a metallocene polyethylene wax, a metallocene polypropylene, a metallocene polyolefin, an oxidized metallocene polyolefin wax, and a metallocene polyolefin wax. More than one of maleic anhydride grafts.
- the coupling agent is one or more selected from the group consisting of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, an isocyanate coupling agent, and a rare earth coupling agent.
- the antioxidant is an antioxidant 1010 and an antioxidant 168, and the mass ratio of the two is 2:1.
- the above method for preparing a plastic reinforcing hemp fiber comprises the following steps:
- Step (1) The mass percentage concentration of the aqueous sodium hydroxide solution is 1% to 10%
- the mass percentage concentration of the hemp fiber treatment agent aqueous solution is 10% to 50%; the dry water is dried by centrifugation; the drying is air drying to a mass moisture content of 8 to 15% (Normal moisture content of hemp fiber).
- Step (1) The drying is performed by vacuum drying, and the drying temperature is 90 to 150. °C, the mass moisture content of the dried to hemp fiber is less than 1%; the rinse with water is washed to pH 7.0 ⁇ 9.0.
- Step (2) the stirring time is 5 to 10 minutes; the stirring speed is 50 to 300 per minute. Turn.
- the principle of the invention is: the invention washes off impurities on the surface of the fiber by using a dilute alkali solution, and then uses urea - Water of a treatment agent such as a formaldehyde resin prepolymer, a trimethylol melamine resin or a hexamethylol melamine resin Solution treatment, the hydroxyl group on the surface of the fiber reacts with the methylol group of the treating agent, and the surface of the fiber is coated with a layer of urea-formaldehyde resin or melamine resin, which reduces the surface polarity of the hemp fiber, reduces the water absorption rate of the hemp fiber, and improves the water absorption rate.
- the rigidity and heat resistance of the hemp fiber; the compatibility of the hemp fiber with the plastic is further improved by the coupling agent, and the lubricity and dispersibility of the fiber interior are improved by the functional polyolefin.
- the short cut hemp fiber prepared by the invention has good color, good rigidity and heat resistance, and can be directly added into the plastic matrix like the short glass fiber, and the phase with the plastic. It has good capacitance and can be used to prepare high-performance short hemp fiber/plastic composite material and play an enhanced role in the plastic matrix.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
A hemp fiber for plastic reinforcement and preparation method thereof are disclosed. The hemp fiber is composed of (by weight): chopped hemp fiber 100 parts, hemp fiber treating agent 0.1-100 parts, functional polyolefin 1-10 parts, coupling agent 0.1-10 parts and antioxidant 0.1-0.5 parts. The method includes the following steps: cutting the chopped hemp fiber off, immersing in sodium hydroxide solution and stirring, washing and spin-drying, immersing in the hemp fiber treating agent aqueous solution, baking and obtaining chopped hemp fiber with treated surface, and then adding the chopped hemp fiber, coupling agent, functional polyolefin and oxidant sequentially into the preheated kneading machine and stirring to obtain the hemp fiber for plastic reinforcement. The chopped hemp fiber prepared herein is superior in terms of color, rigidity, heat resistance, compatibility with plastics, and can be used to prepare high performance composite material of chopped hemp fiber and plastics and can act as reinforcement in plastic matrix.
Description
技术领域 Technical field
本发明属于天然纤维复合材料及木塑复合材料技术领域，具体是指一种塑料增强用麻纤维及其制备方法 The invention belongs to the technical field of natural fiber composite materials and wood plastic composite materials, and particularly relates to a plastic reinforcing hemp fiber and a preparation method thereof
背景技术 Background technique
近几年来，天然植物纤维复合材料及木塑复合材料方面的研究方兴未艾。一方面由于天然植物纤维的来源广泛，价格低廉；另一方面性能方面天然植物纤维增强塑料大有取代矿物纤维增强塑料的趋势。
In recent years, research on natural plant fiber composite materials and wood-plastic composite materials is on the rise. On the one hand, due to the wide range of natural plant fiber sources, the price is low; on the other hand, natural plant fiber reinforced plastics have a tendency to replace mineral fiber reinforced plastics.
多数天然植物纤维是以长纤维状或编制成纤维毡后再与热固性树脂热压成型，不能像玻纤一样直接加入到热塑性塑料中用于注塑成型；同时天然植物纤维一方面由于表面富含羟基，表现出强极性和亲水性，与非极性或弱极性的塑料相容性极差，制备的复合材料的性能差；另一方面由于植物纤维体积大、填充量大，纤维与塑料、纤维与设备及纤维之间的摩擦大使得植物纤维增强塑料难于加工，特别是用于注射成型。为了解决植物纤维与塑料界面相容的问题，目前主要的解决方法就是添加界面相容剂，一类是偶联剂类、如硅烷偶联剂、钛酸酯偶联剂、铝酸酯偶联剂、稀土偶联剂、
异氰酸酯偶联剂等，另一类是马来酸酐与聚烯烃的接枝或共聚物。偶联剂类多数为液体用量少且不容易均匀分散到植物纤维中，影响其偶联效果，工业应用需要特殊的设备来处理；马来酸酐与聚烯烃的接枝或共聚物多数是颗粒状容易分散到塑料和植物纤维中，但其接枝率低难于提高界面粘结力。尽管如此，填充大量的植物纤维和塑料的复合物也给加工带来困难，难于挤出或注射成型。
为了解决植物纤维与塑料复合材料的加工问题，出现各种加工助剂，如烯烃蜡、酰胺蜡、硬脂酸、硬脂酸锌、硬脂酸钙等，但是过多的加工助剂的加入也会使得复合材料的性能下降。
Most natural plant fibers are formed by long-fiber or braided fiber mats and then thermoformed with thermosetting resins. They cannot be directly added to thermoplastics for injection molding like glass fibers. At the same time, natural plant fibers are rich in hydroxyl groups on the one hand. , showing strong polarity and hydrophilicity, poor compatibility with non-polar or weakly polar plastics, poor performance of prepared composites; on the other hand, due to the large volume of plant fibers, large filling capacity, fibers and The large friction between plastics, fibers and equipment and fibers makes plant fiber reinforced plastics difficult to process, especially for injection molding. In order to solve the problem of compatibility between plant fiber and plastic interface, the main solution at present is to add interface compatibilizer, one type is coupling agent, such as silane coupling agent, titanate coupling agent, aluminate coupling. Agent, rare earth coupling agent,
The isocyanate coupling agent and the like, and the other is a graft or copolymer of maleic anhydride and a polyolefin. Most of the coupling agents are used in small amounts of liquid and are not easily dispersed uniformly in plant fibers, affecting the coupling effect. Industrial applications require special equipment to handle; grafts or copolymers of maleic anhydride and polyolefin are mostly particles. The shape is easily dispersed into plastic and plant fibers, but its grafting rate is low and it is difficult to improve the interfacial adhesion. Despite this, filling a large number of composites of plant fibers and plastics presents difficulties in processing and is difficult to extrude or injection mold.
In order to solve the processing problems of plant fiber and plastic composite materials, various processing aids such as olefin wax, amide wax, stearic acid, zinc stearate, calcium stearate, etc., but excessive processing aids are added. It also degrades the performance of the composite.
发明内容 Summary of the invention
为克服上述现有技术中存在的不足，本发明的首要目的在于提供一种塑料增强用麻纤维。 In order to overcome the deficiencies in the prior art described above, it is a primary object of the present invention to provide a hemp fiber for plastic reinforcement.
本发明的另一目的在于提供上述塑料增强用麻纤维的制备方法。 Another object of the present invention is to provide a method for producing the above-mentioned plastic reinforcing hemp fiber.
为实现上述目的，本发明提供如下技术方案：一种塑料增强用麻纤维 ，该 塑料增强用麻纤维
由以下按重量份计的组分组成： In order to achieve the above object, the present invention provides the following technical solution: a hemp fiber for plastic reinforcement, the hemp fiber for plastic reinforcement
It consists of the following components by weight:
短切麻纤维 100 份 Short cut hemp fiber 100 parts
麻纤维处理剂 0.1 ～ 100 份（优选 10 ～ 80 份） Hemp fiber treatment agent 0.1 to 100 parts (preferably 10 to 80 parts)
功能性聚烯烃 1 ～ 10 份 Functional polyolefin 1 to 10 parts
偶联剂 0.1 ～ 10 份 Coupling agent 0.1 to 10 parts
抗氧剂 0.1 ～ 0.5 份。 Antioxidant 0.1 to 0.5 parts.
所述短切麻纤维为苎麻纤维、亚麻纤维、剑麻纤维、黄麻纤维和焦麻纤维中的一种以上。 The short cut hemp fiber is one or more of ramie fiber, flax fiber, sisal fiber, jute fiber, and hemp fiber.
所述麻纤维处理剂为尿素 - 甲醛树脂预聚体、三羟甲基三聚氰胺树脂或六羟甲基三聚氰胺树脂。 The hemp fiber treating agent is a urea-formaldehyde resin prepolymer, a trimethylol melamine resin or a hexamethylol melamine resin.
所述功能性聚烯烃为 茂金属聚乙烯蜡、茂金属聚丙烯、茂金属聚烯烃、氧化茂金属聚烯烃蜡和茂金属聚烯烃蜡 -
马来酸酐接枝物中的一种以上。 The functional polyolefin is a metallocene polyethylene wax, a metallocene polypropylene, a metallocene polyolefin, an oxidized metallocene polyolefin wax, and a metallocene polyolefin wax.
More than one of maleic anhydride grafts.
所述偶联剂为硅烷偶联剂、钛酸酯偶联剂、铝酸酯偶联剂、异氰酸酯偶联剂和稀土偶联剂中的一种以上。 The coupling agent is one or more selected from the group consisting of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, an isocyanate coupling agent, and a rare earth coupling agent.
所述抗氧剂是抗氧剂 1010 和抗氧剂 168 ，两者的质量比为 2 ： 1 。 The antioxidant is an antioxidant 1010 and an antioxidant 168, and the mass ratio of the two is 2:1.
上述的 一种塑料增强用麻纤维的制备方法， 包括以下操作步骤： The above method for preparing a plastic reinforcing hemp fiber comprises the following steps:
（ 1 ）将麻纤维切断至 1 ～ 20mm ，得到短 切麻纤维；将短切麻纤维置于氢氧化钠水溶液中浸泡并搅拌
1 ～ 20min 后，用清水冲洗干净，甩干水份后晾干，再浸泡在温度为 80 ～ 90 ℃的麻纤维处理剂水溶液中 5min ～ 30min
，待麻纤维吸尽麻纤维处理剂水溶液后，烘干，得到经表面处理的短切麻纤维； (1) Cut the hemp fiber to 1 ~ 20mm to obtain short-cut hemp fiber; soak the short-cut hemp fiber in sodium hydroxide solution and stir
After 1 to 20 minutes, rinse with clean water, dry the water, dry it, and soak it in the hemp fiber treatment agent at a temperature of 80 ~ 90 °C for 5min ~ 30min
After the hemp fiber has exhausted the aqueous solution of the hemp fiber treatment agent, it is dried to obtain a surface-treated short-cut hemp fiber;
（ 2 ）将经表面处理的短切麻纤维、偶联剂、功能性聚烯烃和抗氧剂依次加入到预热至 70 ～ 80
℃的捏合机中，搅拌，得到 塑料增强用麻纤维。 (2) The surface treated short-cut hemp fiber, coupling agent, functional polyolefin and antioxidant are sequentially added to preheat to 70-80
The kneading machine at °C was stirred to obtain hemp fiber for plastic reinforcement.
步骤（ 1 ）所述氢氧化钠水溶液的质量百分比浓度为 1% ～ 10%
；所述麻纤维处理剂水溶液的质量百分比浓度为 10% ～ 50% ；所述甩干水份是采用离心方式甩干水分；所述晾干是晾至质量含水率为 8 ～ 15%
（麻纤维的正常含水率）。 Step (1) The mass percentage concentration of the aqueous sodium hydroxide solution is 1% to 10%
The mass percentage concentration of the hemp fiber treatment agent aqueous solution is 10% to 50%; the dry water is dried by centrifugation; the drying is air drying to a mass moisture content of 8 to 15%
(Normal moisture content of hemp fiber).
步骤（ 1 ）所述烘干是采用真空干燥进行烘干，烘干温度为 90 ～ 150
℃，烘干至麻纤维的质量含水率小于 1% ；所述用清水冲洗为冲洗至 pH 7.0 ～ 9.0 。 Step (1) The drying is performed by vacuum drying, and the drying temperature is 90 to 150.
°C, the mass moisture content of the dried to hemp fiber is less than 1%; the rinse with water is washed to pH 7.0 ~ 9.0.
步骤（ 2 ）所述搅拌的时间为 5 ～ 10min ；所述搅拌的速度为每分钟 50 ～ 300
转。 Step (2), the stirring time is 5 to 10 minutes; the stirring speed is 50 to 300 per minute.
Turn.
本发明的原理是：本发明通过稀碱液洗去纤维表面的杂质，再用 尿素 -
甲醛树脂预聚体、三羟甲基三聚氰胺树脂或六羟甲基三聚氰胺树脂等处理剂的水
溶液处理，纤维表面的羟基与处理剂的羟甲基发生反应，在纤维表面包覆上一层脲醛树脂或三聚氰胺树脂，降低了麻纤维的表面极性，减低麻纤维的吸水率，同时提高了麻纤维的刚性和耐热性；再通过偶联剂提高麻纤维与塑料的相容性，及通过功能性聚烯烃改善纤维内部的润滑性和分散性。 The principle of the invention is: the invention washes off impurities on the surface of the fiber by using a dilute alkali solution, and then uses urea -
Water of a treatment agent such as a formaldehyde resin prepolymer, a trimethylol melamine resin or a hexamethylol melamine resin
Solution treatment, the hydroxyl group on the surface of the fiber reacts with the methylol group of the treating agent, and the surface of the fiber is coated with a layer of urea-formaldehyde resin or melamine resin, which reduces the surface polarity of the hemp fiber, reduces the water absorption rate of the hemp fiber, and improves the water absorption rate. The rigidity and heat resistance of the hemp fiber; the compatibility of the hemp fiber with the plastic is further improved by the coupling agent, and the lubricity and dispersibility of the fiber interior are improved by the functional polyolefin.
与现有技术相比，本发明具有如下的有益效果：本发明制备的短切麻纤维色泽好，刚性和耐热性好，可以直接像短玻纤一样加入到塑料基体中，与塑料的相容性好，可用于制备高性能的短麻纤维\塑料复合材料，并在塑料基体中起到增强的作用。
Compared with the prior art, the invention has the following beneficial effects: the short cut hemp fiber prepared by the invention has good color, good rigidity and heat resistance, and can be directly added into the plastic matrix like the short glass fiber, and the phase with the plastic. It has good capacitance and can be used to prepare high-performance short hemp fiber/plastic composite material and play an enhanced role in the plastic matrix.
具体实施方式 detailed description
下面结合实施例对本发明做进一步详细的描述，但本发明的实施方式不限于此。 The present invention will be further described in detail below with reference to the embodiments, but the embodiments of the present invention are not limited thereto.
实施例 1 Example 1
（ 1 ）将 100 重量份苎麻纤维切断至 1 ～ 20mm ，得到短
切麻纤维；将短切麻纤维置于氢氧化钠水溶液（质量百分比浓度为 1% ）中浸泡并搅拌 20min 后，用清水冲洗至 pH 7.0 ，离心甩干水份，再浸泡在温度为
80 ℃的麻纤维处理剂（ 80 重量份尿素 - 甲醛树脂预聚体）水溶液（质量百分比浓度为 30% ）中处理 30min
，待麻纤维吸尽麻纤维处理剂水溶液后采用温度 110 ℃真空干燥至麻纤维质量含水率小于 1% ，得到经表面处理的短切麻纤维； (1) Cut 100 parts by weight of ramie fiber to 1 to 20 mm to get short
Cut the hemp fiber; soak the short cut hemp fiber in an aqueous sodium hydroxide solution (concentration of 1% by mass) and stir for 20 minutes, rinse with water to pH 7.0, centrifuge to dry the water, and then soak at the temperature.
80 °C hemp fiber treatment agent (80 parts by weight urea-formaldehyde resin prepolymer) aqueous solution (30% by mass concentration) for 30min
After the hemp fiber has exhausted the aqueous solution of the hemp fiber treatment agent, it is vacuum dried at a temperature of 110 ° C until the mass moisture content of the hemp fiber is less than 1%, and the surface treated short cut hemp fiber is obtained;
（ 2 ）将经表面处理的短切麻纤维、 2 重量份硅烷偶联剂、 9 重量份功能性聚烯烃（ 5 重量份
茂金属聚乙烯蜡和 4 重量份 茂金属聚烯烃蜡 - 马来酸酐接枝物混合 ）和 0.4 重量份抗氧剂（抗氧剂 1010 和抗氧剂 168 ，两者的质量比为 2 ：
1 ）依次加入到预热至 70 ℃的捏合机中，以每分钟 100 转的速度搅拌 5min ，得到
塑料增强用麻纤维；所得塑料增强用麻纤维色泽淡黄，刚挺，容易分散到树脂中不抱团。 (2) Surface treated short cut hemp fiber, 2 parts by weight of silane coupling agent, 9 parts by weight of functional polyolefin (5 parts by weight)
Metallocene polyethylene wax and 4 parts by weight of metallocene polyolefin wax - maleic anhydride graft mixed) and 0.4 parts by weight of antioxidant (antioxidant 1010 and antioxidant 168, the mass ratio of the two is 2:
1) sequentially added to a kneading machine preheated to 70 ° C, and stirred at a speed of 100 rpm for 5 minutes to obtain
Hemp fiber for plastic reinforcement; the resulting plastic reinforcing hemp fiber is light yellow, rigid, and easy to disperse into the resin without clumping.
实施例 2 Example 2
（ 1 ）将 100 重量份亚麻纤维切断至 1 ～ 20mm ，得到短
切麻纤维；将短切麻纤维置于氢氧化钠水溶液（质量百分比浓度为 10% ）中浸泡并搅拌 2min 后，用清水冲洗至 pH 9.0 ，离心甩干水份，再浸泡在温度为
90 ℃的麻纤维处理剂（ 90 重量份三羟甲基三聚氰胺树脂）水溶液（质量百分比浓度为 20% ）中 30min ，待麻纤维吸尽麻纤维处理剂水溶液后，采用温度
150 ℃真空干燥至麻纤维含水率小于 1% ，得到经表面处理的短切麻纤维； (1) Cut 100 parts by weight of flax fiber to 1 to 20 mm to get short
Cut the hemp fiber; soak the short cut hemp fiber in an aqueous sodium hydroxide solution (10% by mass) and stir for 2 minutes, rinse with water to pH 9.0, centrifuge to dry the water, and then soak at the temperature.
90 °C hemp fiber treatment agent (90 parts by weight of trimethylol melamine resin) aqueous solution (20% by mass concentration) for 30 minutes, after the hemp fiber exhausted the hemp fiber treatment agent aqueous solution, the temperature was adopted.
Vacuum drying at 150 °C until the moisture content of the hemp fiber is less than 1%, and the surface treated short cut hemp fiber is obtained;
（ 2 ）将经表面处理的短切麻纤维、 8 重量份偶联剂（ 4 重量份钛酸酯偶联剂和 4
重量份稀土偶联剂混合）、 4 重量份功能性聚烯烃（ 2 重量份 茂金属聚丙烯和 2 重量份 茂金属聚烯烃混合 ）和 0.5 重量份抗氧剂（抗氧剂 1010
和抗氧剂 168 ，两者的质量比为 2 ： 1 ）依次加入到预热至 80 ℃的捏合机中，以每分钟 50 转的速度搅拌 10min ，得到
塑料增强用麻纤维；所得塑料增强用麻纤维色泽淡黄，刚挺，容易分散到树脂中不抱团。 (2) Surface treated short cut hemp fiber, 8 parts by weight of coupling agent (4 parts by weight of titanate coupling agent and 4
Parts by weight of rare earth coupling agent), 4 parts by weight of functional polyolefin (2 parts by weight of metallocene polypropylene and 2 parts by weight of metallocene polyolefin) and 0.5 parts by weight of antioxidant (antioxidant 1010)
And the antioxidant 168, the mass ratio of the two is 2: 1), sequentially added to the kneading machine preheated to 80 °C, and stirred at 50 rpm for 10 min to obtain
Hemp fiber for plastic reinforcement; the resulting plastic reinforcing hemp fiber is light yellow, rigid, and easy to disperse into the resin without clumping.
实施例 3 Example 3
（ 1 ）将 100 重量份剑麻纤维切断至 1 ～ 20mm ，得到短
切麻纤维；将短切麻纤维置于氢氧化钠水溶液（质量百分比浓度为 5% ）中浸泡并搅拌 5min 后，用清水冲洗至 pH 8.0 ，离心甩干水份，再浸泡在温度为
85 ℃的麻纤维处理剂（ 100 重量份六羟甲基三聚氰胺树脂）水溶液（质量百分比浓度为 10% ）中处理 20min
，待麻纤维吸尽麻纤维处理剂水溶液后，采用温度 120 ℃真空干燥至麻纤维质量含水率小于 1% ，得到经表面处理的短切麻纤维； (1) Cut 100 parts by weight of sisal fiber to 1 to 20 mm to get short
Cut the hemp fiber; soak the short cut hemp fiber in aqueous sodium hydroxide solution (5% by mass) and stir for 5 minutes, rinse with water to pH 8.0, centrifuge to dry the water, and then soak at the temperature
Treatment at 85 °C in an aqueous solution of hemp fiber treatment (100 parts by weight of hexamethylol melamine resin) (10% by mass)
After the hemp fiber has exhausted the aqueous solution of the hemp fiber treatment agent, the vacuum is dried at a temperature of 120 ° C until the mass moisture content of the hemp fiber is less than 1%, and the surface-treated short-cut hemp fiber is obtained;
（ 2 ）将经表面处理的短切麻纤维、 7 重量份偶联剂（ 5 重量份铝酸酯偶联剂和 2
重量份异氰酸酯偶联剂）、 7 重量份功能性聚烯烃（ 5 重量份 茂金属聚烯烃和 2 重量份 氧化茂金属聚烯烃蜡混合 ）和 0.4 重量份抗氧剂（抗氧剂
1010 和抗氧剂 168 ，两者的质量比为 2 ： 1 ）依次加入到预热至 75 ℃的捏合机中，以每分钟 300 转的速度搅拌 5min ，得到
塑料增强用麻纤维；所得塑料增强用麻纤维色泽淡黄，刚挺，容易分散到树脂中不抱团。 (2) Surface treated short cut hemp fiber, 7 parts by weight of coupling agent (5 parts by weight of aluminate coupling agent and 2
Parts by weight of isocyanate coupling agent), 7 parts by weight of functional polyolefin (5 parts by weight of metallocene polyolefin and 2 parts by weight of metallocene polyolefin wax) and 0.4 parts by weight of antioxidant (antioxidant)
1010 and antioxidant 168, the mass ratio of the two is 2: 1), sequentially added to the kneading machine preheated to 75 °C, and stirred at 300 rpm for 5 min to obtain
Hemp fiber for plastic reinforcement; the resulting plastic reinforcing hemp fiber is light yellow, rigid, and easy to disperse into the resin without clumping.
实施例 4 Example 4
（ 1 ）将 100 重量份黄麻纤维切断至 1 ～ 20mm ，得到短
切麻纤维；将短切麻纤维置于氢氧化钠水溶液（质量百分比浓度为 3% ）中浸泡并搅拌 1min 后，用清水冲洗至 pH 7.5 ，离心甩干水份，再浸泡在温度为
88 ℃的麻纤维处理剂（ 50 重量份尿素 - 甲醛树脂预聚体）水溶液（质量百分比浓度为 30% ）中处理 25min
，待麻纤维吸尽麻纤维处理剂水溶液后，采用温度 100 ℃真空干燥至麻纤维质量含水率小于 1% ，得到经表面处理的短切麻纤维； (1) Cut 100 parts by weight of jute fiber to 1 to 20 mm to get short
Cut the hemp fiber; soak the short cut hemp fiber in aqueous sodium hydroxide solution (3% by mass) and stir for 1 min, rinse with water to pH 7.5, centrifuge to dry the water, and then soak at the temperature.
Treatment of 88 °C hemp fiber treatment agent (50 parts by weight urea-formaldehyde resin prepolymer) aqueous solution (30% by mass concentration) for 25 min
After the hemp fiber has exhausted the aqueous solution of the hemp fiber treatment agent, the vacuum is dried at a temperature of 100 ° C until the mass moisture content of the hemp fiber is less than 1%, and the surface treated short cut hemp fiber is obtained;
（ 2 ）将经表面处理的短切麻纤维、 8 重量份偶联剂（ 5 重量份异氰酸酯偶联剂和 3
重量份稀土偶联剂混合）、 1 重量份 氧化茂金属聚烯烃蜡 和 0.3 重量份抗氧剂（抗氧剂 1010 和抗氧剂 168 ，两者的质量比为 2 ： 1
）依次加入到预热至 78 ℃的捏合机中，以每分钟 150 转的速度搅拌 8min ，得到
塑料增强用麻纤维；所得塑料增强用麻纤维色泽淡黄，刚挺，容易分散到树脂中不抱团。 (2) Surface treated short cut hemp fiber, 8 parts by weight of coupling agent (5 parts by weight of isocyanate coupling agent and 3
1 part by weight of the oxidized metallocene polyolefin wax and 0.3 parts by weight of the antioxidant (antioxidant 1010 and antioxidant 168, the mass ratio of the two is 2:1)
) was sequentially added to a kneading machine preheated to 78 ° C, and stirred at a speed of 150 rpm for 8 minutes to obtain
Hemp fiber for plastic reinforcement; the resulting plastic reinforcing hemp fiber is light yellow, rigid, and easy to disperse into the resin without clumping.
实施例 5 Example 5
（ 1 ）将 100 重量份焦麻纤维切断至 1 ～ 20mm ，得到短
切麻纤维；将短切麻纤维置于氢氧化钠水溶液（质量百分比浓度为 8% ）中浸泡并搅拌 15min 后，用清水冲洗至 pH 8.5 ，离心甩干水份，再浸泡在温度为
80 ℃的麻纤维处理剂（ 20 重量份三羟甲基三聚氰胺树脂）水溶液（质量百分比浓度为 50% ）中处理 15min
，待麻纤维吸尽麻纤维处理剂水溶液后，采用温度 90 ℃真空干燥至麻纤维质量含水率小于 1% ，得到经表面处理的短切麻纤维； (1) Cut 100 parts by weight of hemp fiber to 1 to 20 mm to get short
Cut the hemp fiber; soak the short cut hemp fiber in an aqueous sodium hydroxide solution (8% by mass) and stir for 15 minutes, rinse with water to pH 8.5, centrifuge to dry the water, and then soak at the temperature.
Treatment with an aqueous solution of hemp fiber treatment agent (20 parts by weight of trimethylol melamine resin) at 80 °C (50% by mass concentration) for 15 min
After the hemp fiber has exhausted the aqueous solution of the hemp fiber treatment agent, the vacuum is dried at a temperature of 90 ° C until the mass moisture content of the hemp fiber is less than 1%, and the surface treated short cut hemp fiber is obtained;
（ 2 ）将经表面处理的短切麻纤维、 0.1 重量份异氰酸酯偶联剂、 5 重量份功能性聚烯烃（ 1 重量份
茂金属聚乙烯蜡、 2 重量份 茂金属聚丙烯和 3 重量份 茂金属聚烯烃蜡 - 马来酸酐接枝物混合 ）和 0.1 重量份抗氧剂（抗氧剂 1010 和抗氧剂
168 ，两者的质量比为 2 ： 1 ）依次加入到预热至 76 ℃的捏合机中，以每分钟 250 转的速度搅拌 8min ，得到
塑料增强用麻纤维；所得塑料增强用麻纤维色泽淡黄，刚挺，容易分散到树脂中不抱团。 (2) Surface treated short cut hemp fiber, 0.1 part by weight of isocyanate coupling agent, and 5 parts by weight of functional polyolefin (1 part by weight)
Metallocene polyethylene wax, 2 parts by weight of metallocene polypropylene and 3 parts by weight of metallocene polyolefin wax - maleic anhydride graft mixed) and 0.1 parts by weight of antioxidant (antioxidant 1010 and antioxidant)
168, the mass ratio of the two is 2: 1), sequentially added to the kneading machine preheated to 76 °C, and stirred at a speed of 250 rpm for 8 minutes.
Hemp fiber for plastic reinforcement; the resulting plastic reinforcing hemp fiber is light yellow, rigid, and easy to disperse into the resin without clumping.
实施例 6 Example 6
（ 1 ）将 100 重量份麻纤维（苎麻纤维和焦麻纤维混合）以上切断至 1 ～ 20mm ，得到短
切麻纤维；将短切麻纤维置于氢氧化钠水溶液（质量百分比浓度为 6% ）中浸泡并搅拌 12min 后，用清水冲洗至 pH 7.5 ，离心甩干水份，再浸泡在温度为
90 ℃的麻纤维处理剂（ 50 重量份六羟甲基三聚氰胺树脂）水溶液（质量百分比浓度为 30% ）中处理 5min ，待麻纤维吸尽麻纤维处理剂水溶液后，采用温度
150 ℃真空干燥至麻纤维质量含水率小于 1% ，得到经表面处理的短切麻纤维； (1) Cut 100 parts by weight of hemp fiber (mixed ramie fiber and hemp fiber) to 1 to 20 mm to get short
Cut the hemp fiber; soak the short cut hemp fiber in an aqueous sodium hydroxide solution (6% by mass concentration) and stir for 12 minutes, rinse with water to pH 7.5, centrifuge to dry the water, and then soak at the temperature.
90 °C hemp fiber treatment agent (50 parts by weight of hexamethylol melamine resin) aqueous solution (30% by mass concentration) for 5 min, after the hemp fiber exhausted the hemp fiber treatment agent aqueous solution, the temperature was adopted.
Vacuum drying at 150 °C until the mass moisture content of the hemp fiber is less than 1%, and the surface treated short cut hemp fiber is obtained;
（ 2 ）将经表面处理的短切麻纤维、 10 重量份偶联剂（ 2 重量份硅烷偶联剂、 5
重量份铝酸酯偶联剂和 3 重量份稀土偶联剂混合）、 10 重量份功能性聚烯烃（ 2 重量份 茂金属聚乙烯蜡、 3 重量份 茂金属聚丙烯、 2 重量份
茂金属聚烯烃和 3 重量份 氧化茂金属聚烯烃蜡 ）和 0.5 重量份抗氧剂（抗氧剂 1010 和抗氧剂 168 ，两者的质量比为 2 ： 1
）依次加入到预热至 72 ℃的捏合机中，以每分钟 280 转的速度搅拌 7min ，得到
塑料增强用麻纤维；所得塑料增强用麻纤维色泽淡黄，刚挺，容易分散到树脂中不抱团。 (2) Surface treated short cut hemp fiber, 10 parts by weight of coupling agent (2 parts by weight of silane coupling agent, 5
10 parts by weight of functional polyolefin (2 parts by weight of metallocene polyethylene wax, 3 parts by weight of metallocene polypropylene, 2 parts by weight)
Metallocene polyolefin and 3 parts by weight of oxidized metallocene polyolefin wax) and 0.5 parts by weight of antioxidant (antioxidant 1010 and antioxidant 168, the mass ratio of the two is 2:1)
) was sequentially added to a kneading machine preheated to 72 ° C, and stirred at 280 rpm for 7 min to obtain
Hemp fiber for plastic reinforcement; the resulting plastic reinforcing hemp fiber is light yellow, rigid, and easy to disperse into the resin without clumping.
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and combinations thereof may be made without departing from the spirit and scope of the invention. Simplifications should all be equivalent replacements and are included in the scope of the present invention.
Claims (10)
- 一种塑料增强用麻纤维，其特征在于：该塑料增强用麻纤维由以下按重量份计的组分组成： A hemp fiber for plastic reinforcement, characterized in that the hemp fiber for plastic reinforcement is composed of the following components by weight:短切麻纤维 100份 Short cut hemp fiber 100 parts麻纤维处理剂 0.1～100份Hemp fiber treatment agent 0.1～100 parts功能性聚烯烃 1～10份Functional polyolefin 1 to 10 parts偶联剂 0.1～10份Coupling agent 0.1~10 parts抗氧剂 0.1～0.5份。Antioxidant 0.1 to 0.5 parts.
- 根据权利要求1所述的一种塑料增强用麻纤维，其特征在于：所述短切麻纤维为苎麻纤维、亚麻纤维、剑麻纤维、黄麻纤维和焦麻纤维中的一种以上。The hemp fiber for plastic reinforcement according to claim 1, wherein the short cut hemp fiber is one or more of ramie fiber, flax fiber, sisal fiber, jute fiber, and hemp fiber.
- 根据权利要求1所述的一种塑料增强用麻纤维，其特征在于：所述麻纤维处理剂为尿素-甲醛树脂预聚体、三羟甲基三聚氰胺树脂或六羟甲基三聚氰胺树脂。The hemp fiber for plastic reinforcement according to claim 1, wherein the hemp fiber treating agent is a urea-formaldehyde resin prepolymer, a trimethylol melamine resin or a hexamethylol melamine resin.
- 根据权利要求1所述的一种塑料增强用麻纤维，其特征在于：所述功能性聚烯烃为茂金属聚乙烯蜡、茂金属聚丙烯、茂金属聚烯烃、氧化茂金属聚烯烃蜡和茂金属聚烯烃蜡-马来酸酐接枝物中的一种以上。The hemp fiber for plastic reinforcement according to claim 1, wherein the functional polyolefin is a metallocene polyethylene wax, a metallocene polypropylene, a metallocene polyolefin, an oxidized metallocene polyolefin wax, and a molybdenum. One or more of metal polyolefin wax-maleic anhydride grafts.
- 根据权利要求1所述的一种塑料增强用麻纤维，其特征在于：所述偶联剂为硅烷偶联剂、钛酸酯偶联剂、铝酸酯偶联剂、异氰酸酯偶联剂和稀土偶联剂中的一种以上。The hemp fiber for plastic reinforcement according to claim 1, wherein the coupling agent is a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, an isocyanate coupling agent, and a rare earth More than one of the coupling agents.
- 根据权利要求1所述的一种塑料增强用麻纤维，其特征在于：所述抗氧剂是抗氧剂1010和抗氧剂168，两者的质量比为2：1。The hemp fiber for plastic reinforcement according to claim 1, wherein the antioxidant is an antioxidant 1010 and an antioxidant 168, and the mass ratio of the two is 2:1.
- 据权利要求1所述的一种塑料增强用麻纤维的制备方法，其特征在于包括以下操作步骤：A method of preparing a hemp fiber for plastic reinforcement according to claim 1, comprising the steps of:（1）将麻纤维切断至1～20mm，得到短切麻纤维；将短切麻纤维置于氢氧化钠水溶液中浸泡并搅拌1～20min后，用清水冲洗，甩干水份后晾干，再浸泡在温度为80～90℃的麻纤维处理剂水溶液中5min～30min，待麻纤维吸尽麻纤维处理剂水溶液后烘干，得到经表面处理的短切麻纤维；(1) Cutting the hemp fiber to 1-20 mm to obtain short cut hemp fiber; soaking the short cut hemp fiber in sodium hydroxide aqueous solution and stirring for 1-20 min, rinse with water, dry the water, and dry it. Soaking in an aqueous solution of hemp fiber treatment agent at a temperature of 80-90 ° C for 5 min to 30 min, and drying the hemp fiber after exhausting the aqueous solution of the hemp fiber treatment agent to obtain a surface-treated short-cut hemp fiber;（2）将经表面处理的短切麻纤维、偶联剂、功能性聚烯烃和抗氧剂依次加入到预热至70～80℃的捏合机中，搅拌，得到塑料增强用麻纤维。(2) The surface-treated short-cut hemp fiber, the coupling agent, the functional polyolefin, and the antioxidant are sequentially added to a kneader preheated to 70 to 80 ° C, and stirred to obtain a hemp fiber for plastic reinforcement.
- 根据权利要求7所述的制备方法，其特征在于：步骤（1）所述氢氧化钠水溶液的质量百分比浓度为1%～10%；所述麻纤维处理剂水溶液的质量百分比浓度为10%～50%；所述甩干水份是采用离心方式甩干水分；所述晾干是晾至质量含水率为8～15%。The preparation method according to claim 7, wherein the mass percentage concentration of the aqueous sodium hydroxide solution in the step (1) is 1% to 10%; and the mass percentage concentration of the aqueous solution of the hemp fiber treatment agent is 10%. 50%; the dry water is dried by centrifugation; the air drying is air to a mass moisture content of 8 to 15%.
- 根据权利要求7所述的制备方法，其特征在于：步骤（1）所述烘干是采用真空干燥进行烘干，烘干温度为90～150℃，烘干至质量含水率小于1%；所述用清水冲洗为冲洗至pH 7.0～9.0。The preparation method according to claim 7, wherein the drying in the step (1) is performed by vacuum drying, the drying temperature is 90 to 150 ° C, and the drying to a mass moisture content is less than 1%; Rinse with water to rinse to pH 7.0 to 9.0.
- 根据权利要求7所述的制备方法，其特征在于：步骤（2）所述搅拌的时间为5～10min；所述搅拌的速度为每分钟50～300转。The preparation method according to claim 7, wherein the stirring time in the step (2) is 5 to 10 minutes; and the stirring speed is 50 to 300 revolutions per minute.
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| CN2010800029527A CN102232099B (en) | 2010-05-12 | 2010-05-12 | Fibrilia for plastic reinforcing and method for manufacturing the same |
| PCT/CN2010/072652 WO2011140706A1 (en) | 2010-05-12 | 2010-05-12 | Hemp fiber for plastic reinforcement and preparation method thereof |
| KR1020127000061A KR101350949B1 (en) | 2010-05-12 | 2010-05-12 | Hemp fiber for plastic reinforcement and preparation method thereof |
| US13/321,658 US20120070663A1 (en) | 2010-05-12 | 2010-05-12 | Bast fibers for plastics reinforcement and preparation method thereof |
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| PCT/CN2010/072652 WO2011140706A1 (en) | 2010-05-12 | 2010-05-12 | Hemp fiber for plastic reinforcement and preparation method thereof |
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| WO2016027848A1 (en) * | 2014-08-20 | 2016-02-25 | 北川工業株式会社 | Flame-retardancy-imparting material and flame-retardant resin molded article |
| KR101715317B1 (en) * | 2015-10-05 | 2017-03-22 | 주식회사 서연이화 | Foam composition and manufacturing method of the same |
| CN106079723B (en) * | 2016-06-24 | 2018-08-31 | 浙江大学宁波理工学院 | Flame-retardant modified ramie fabric/benzoxazine colophony laminate and preparation method thereof |
| CN107012587A (en) * | 2017-05-15 | 2017-08-04 | 吉林大学 | A kind of natural environmental-protective type flaxen fiber enhancing degradable polyalcohol group felt material and its composite board and preparation method |
| CN110219163B (en) * | 2019-04-30 | 2021-12-21 | 江阴芗菲纺织科技有限公司 | Method for pretreating pure linen yarn by alkali-urea |
| CN114015122A (en) * | 2021-11-23 | 2022-02-08 | 广东富强科技股份有限公司 | Automobile ceiling base material and preparation method thereof |
| CN114561058B (en) * | 2022-04-02 | 2022-12-06 | 深圳市兴昌明印刷制品有限公司 | High-density PE and application thereof in human body sensing panel |
| CN114621539B (en) * | 2022-04-25 | 2023-05-02 | 上饶市博美新材料有限公司 | Heat-resistant composite plastic and preparation method thereof |
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| US20120070663A1 (en) | 2012-03-22 |
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