CN118087080A - Polypropylene fiber material and preparation method and application thereof - Google Patents
Polypropylene fiber material and preparation method and application thereof Download PDFInfo
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- CN118087080A CN118087080A CN202410479205.6A CN202410479205A CN118087080A CN 118087080 A CN118087080 A CN 118087080A CN 202410479205 A CN202410479205 A CN 202410479205A CN 118087080 A CN118087080 A CN 118087080A
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- -1 Polypropylene Polymers 0.000 title claims abstract description 174
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 148
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 148
- 239000002657 fibrous material Substances 0.000 title claims abstract description 111
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 239000010410 layer Substances 0.000 claims abstract description 211
- 229920005989 resin Polymers 0.000 claims abstract description 202
- 239000011347 resin Substances 0.000 claims abstract description 202
- 239000002994 raw material Substances 0.000 claims abstract description 50
- 239000000378 calcium silicate Substances 0.000 claims abstract description 27
- 229910052918 calcium silicate Inorganic materials 0.000 claims abstract description 27
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims abstract description 27
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 25
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 25
- 239000002667 nucleating agent Substances 0.000 claims abstract description 23
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims abstract description 22
- 239000012792 core layer Substances 0.000 claims abstract description 18
- 229920005629 polypropylene homopolymer Polymers 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 75
- 239000004567 concrete Substances 0.000 claims description 74
- 230000003078 antioxidant effect Effects 0.000 claims description 58
- 238000009987 spinning Methods 0.000 claims description 35
- 239000000314 lubricant Substances 0.000 claims description 20
- 238000001125 extrusion Methods 0.000 claims description 19
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 16
- 238000005469 granulation Methods 0.000 claims description 15
- 230000003179 granulation Effects 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000000155 melt Substances 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 6
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 6
- 150000007970 thio esters Chemical class 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000002787 reinforcement Effects 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 7
- 239000000835 fiber Substances 0.000 description 71
- 230000000052 comparative effect Effects 0.000 description 30
- 239000000463 material Substances 0.000 description 27
- 239000003513 alkali Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- LNKJESSHRFPVPE-UHFFFAOYSA-N 5-(diethylamino)pentyl 3,4,5-trimethoxybenzoate;hydrochloride Chemical compound Cl.CCN(CC)CCCCCOC(=O)C1=CC(OC)=C(OC)C(OC)=C1 LNKJESSHRFPVPE-UHFFFAOYSA-N 0.000 description 7
- 239000004568 cement Substances 0.000 description 6
- 239000012752 auxiliary agent Substances 0.000 description 4
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011210 fiber-reinforced concrete Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Multicomponent Fibers (AREA)
Abstract
The invention provides a polypropylene fiber material, which comprises a core layer and a skin layer positioned at the periphery of the core layer, wherein the skin layer is made of outer-layer structural resin, and the core layer is made of inner-layer structural resin; the outer layer structural resin is prepared from preparation raw materials comprising homopolypropylene, ethylene acrylic acid copolymer, calcium silicate whisker and nucleating agent; the inner layer structure resin is prepared from preparation raw materials comprising polyethylene terephthalate and glycidyl methacrylate grafted polypropylene; the outer layer structural resin accounts for 20-50% of the total mass of the polypropylene fiber material, and the inner layer structural resin accounts for 50-80% of the total mass of the polypropylene fiber material. The polypropylene fiber material with high corrosion resistance, high interface binding force and high mechanical property is provided by the method.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a polypropylene fiber material and a preparation method and application thereof.
Background
The polypropylene fiber has the characteristics of light weight, high tensile strength and low cost, has almost zero moisture regain, good hydrophobic and moisture-conducting performance, and better acid-base resistance and thermal aging resistance, and can improve the cracking resistance, the impermeability and the wear resistance of the concrete when applied to the concrete.
In order to fully exert the reinforcing effect of the fiber in the concrete, the fiber not only has excellent mechanical properties, but also needs to be well dispersed in the concrete, and meanwhile, the interfacial force between the fiber and the concrete is also an important factor influencing the performance of the concrete. Only if the interface bonding of the fiber and the concrete is sufficient, the reinforcing effect of the fiber can be fully exerted. However, the polypropylene fiber has low surface polarity and hydrophobic surface, is not suitable for being dispersed in concrete, has poor binding force with the concrete, and greatly influences the performance of the polypropylene fiber reinforced concrete.
The polyethylene terephthalate fiber is applied to the field of concrete reinforcement, and has excellent mechanical properties and interface bonding capability compared with polypropylene fiber, but is easy to hydrolyze in a strong alkaline environment of concrete, so that the mechanical properties of the final material are poor, and the application of the polyethylene terephthalate fiber reinforced concrete is influenced.
Therefore, a polypropylene fiber material with high corrosion resistance, high interfacial binding force and high mechanical property is required to be developed in the field of concrete reinforcement so as to solve the technical defects of the existing material.
Disclosure of Invention
The invention provides a polypropylene fiber material, a preparation method and application thereof, and the polypropylene fiber material is applied to the field of concrete reinforcement and has high corrosion resistance, high interface binding force and high mechanical property.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
The first aspect of the invention provides a polypropylene fiber material, which comprises a core layer and a skin layer positioned at the periphery of the core layer, wherein the material of the skin layer is outer layer structural resin, and the material of the core layer is inner layer structural resin; the outer layer structural resin is prepared from preparation raw materials comprising homopolypropylene, ethylene acrylic acid copolymer, calcium silicate whisker and nucleating agent; the inner layer structure resin is prepared from preparation raw materials comprising polyethylene terephthalate and glycidyl methacrylate grafted polypropylene; the outer layer structural resin accounts for 20-50% of the total mass of the polypropylene fiber material, and the inner layer structural resin accounts for 50-80% of the total mass of the polypropylene fiber material.
The polypropylene fiber material provided by the invention has a double-layer structure of a core layer and a skin layer, meanwhile, an outer-layer structural resin prepared based on homo-polypropylene, ethylene acrylic acid copolymer, calcium silicate whisker and a nucleating agent is used in the skin layer structure, an inner-layer structural resin based on polyethylene terephthalate and glycidyl methacrylate grafted polypropylene is used in the core layer structure, and the outer-layer structural resin and the inner-layer structural resin have specific mass ratio.
In the polypropylene fiber material, the outer layer structural resin is matched with homo-polypropylene, ethylene acrylic acid copolymer, calcium silicate whisker and nucleating agent, wherein the calcium silicate whisker is easy to generate hydration reaction with concrete; the ethylene acrylic acid copolymer can improve the dispersion performance of the calcium silicate whisker in the polypropylene resin, can also improve the surface polarity of the polypropylene resin, and is matched with the calcium silicate whisker to be used for improving the interfacial bonding capability of the polypropylene fiber material and the concrete; preferably, the beta nucleating agent is introduced in a matched manner, so that the toughness of the homo-polypropylene material can be further improved.
In the polypropylene fiber material, polyethylene terephthalate and glycidyl methacrylate grafted polypropylene are matched in the preparation raw materials of the inner layer structure resin, and the carboxyl functional group of the polyethylene terephthalate and the glycidyl methacrylate functional group undergo ring opening reaction, so that the compatibility and interface binding force of the inner layer structure resin and the outer layer structure resin are improved.
The polypropylene fiber material adopts the specific outer layer structural resin and the inner layer structural resin to be combined according to the skin-core double-layer structure, the outer layer structural resin has excellent concrete corrosion resistance, and the problem that polyethylene terephthalate resin used by the inner layer structural resin is easy to hydrolyze when meeting concrete can be solved, so that the comprehensive mechanical property and the durability of the polypropylene fiber material in the concrete are improved.
In the polypropylene fiber material provided by the invention, the total mass of the outer layer structural resin and the polypropylene fiber material is controlled to be 20-50%, the total mass of the inner layer structural resin and the polypropylene fiber material is controlled to be 50-80%, and the concrete corrosion resistance of the skin layer structure is fully exerted by controlling the mass content of the outer layer structural resin and the inner layer structural resin, so that the interface bonding capability with concrete is improved, the high mechanical property of the core layer structure is exerted, and the strength of the concrete is improved.
In some embodiments, an auxiliary agent is added to the preparation raw materials of the outer layer structure resin and the inner layer structure resin, wherein the auxiliary agent added to the preparation raw materials of the outer layer structure resin comprises an antioxidant and a lubricant; the auxiliary agent added in the raw materials for preparing the inner layer structure resin comprises an antioxidant and a lubricant; the addition of the auxiliary agent is beneficial to the preparation of the polypropylene fiber material with better comprehensive mechanical property and durability.
In some preferred embodiments, in the preparation raw materials of the outer layer structural resin, the amount of the homo-polypropylene is 75-88 parts by weight, the amount of the ethylene acrylic acid copolymer is 5-10 parts by weight, the amount of the calcium silicate whisker is 5-15 parts by weight, and the amount of the nucleating agent is 0.1-0.5 part by weight; in the preparation raw materials of the inner layer structure resin, the dosage of polyethylene terephthalate is 79-89 parts by weight, and the dosage of glycidyl methacrylate grafted polypropylene is 10-20 parts by weight;
preferably, the preparation raw materials of the outer layer structural resin further comprise: antioxidants and lubricants; further preferably, in the raw materials for preparing the outer layer structural resin, the antioxidant and the lubricant are respectively 0.2-0.5 part by weight and 0.2-0.5 part by weight in sequence;
preferably, the preparation raw materials of the inner layer structure resin further comprise: antioxidants and lubricants; further preferably, in the raw materials for preparing the inner layer structural resin, the antioxidant and the lubricant are respectively 0.2-0.5 part by weight and 0.2-0.5 part by weight in sequence.
In some preferred embodiments, the melt index of the homo-polypropylene used to prepare the outer structural resin is 20-50 g/10min (230 ℃,2.16 kg), and the use of the homo-polypropylene with a preferred melt index is advantageous for improving spinning efficiency.
In some preferred embodiments, the ethylene acrylic acid copolymer used to prepare the outer structural resin has a melt index of 5-20 g/10min (190 ℃,2.16 kg) and a mass content of acrylic acid of 5-22%.
In some preferred embodiments, the laser diffraction particle diameter D50 of the calcium silicate whisker used for preparing the outer layer structural resin is less than or equal to 7um; the nucleating agent used for preparing the outer layer structural resin is polypropylene beta nucleating agent.
In some preferred embodiments, the antioxidants used to prepare the outer structural resin include primary antioxidants and secondary antioxidants, the primary antioxidants being hindered phenolic antioxidants, such as one or more of 1010, 1076 of Li Anlong, 1330 of basf, etc. of the new chemistry; the auxiliary antioxidant is phosphite antioxidant and/or thioester antioxidant, such as one or more of 168 of Xinxiu chemical, DSTDP of Xinxiu chemical, 126 of Basoff, etc.; the mass ratio of the main antioxidant to the auxiliary antioxidant is 1: 1-2: 1, a step of; and/or the lubricant used for preparing the outer layer structure resin is any one or more of zinc stearate and ethylene bis-stearamide; and/or the antioxidants used for preparing the inner layer structure resin comprise a main antioxidant and an auxiliary antioxidant, wherein the main antioxidant is one or more of hindered phenol antioxidants, such as 1010, 1076 of New Xiuchemical, li Anlong, 1330 of Basoff and the like; the auxiliary antioxidant is phosphite antioxidant and/or thioester antioxidant, such as one or more of 168 of Xinxiu chemical, DSTDP of Xinxiu chemical, 126 of Basoff, etc.; the mass ratio of the main antioxidant to the auxiliary antioxidant is 1: 1-2: 1, a step of; and/or the lubricant used for preparing the inner layer structure resin is any one or more of zinc stearate and ethylene bis stearamide.
In some preferred embodiments, the polyethylene terephthalate used to prepare the inner structural resin has an intrinsic viscosity of 0.60-0.85 dL/g as measured according to GB/T14190 and a carboxyl end group content of 20-30 mol/T as measured according to FZ/T50012, and the polyethylene terephthalate with a preferred viscosity range is used to further improve the spinnability of the resulting polypropylene fiber material and has further improved mechanical properties.
In some preferred embodiments, the melt index of the glycidyl methacrylate grafted polypropylene used for preparing the inner structural resin is 10-25 g/10min (190 ℃,2.16 kg), the grafting rate of the glycidyl methacrylate is 0.5-2%, and the preferable melt index range of the glycidyl methacrylate grafted polypropylene is adopted, so that the dispersion uniformity in polyethylene terephthalate is further improved.
The second aspect of the invention provides a preparation method of the polypropylene fiber material, which comprises the following steps:
(1) The preparation raw materials of the outer layer structure resin are placed in a double-screw extruder for melt dispersion and extrusion granulation to obtain the outer layer structure resin, and the length-diameter ratio of the screw of the double-screw extruder is preferably (40-52): 1, the rotating speed of the screw is 100-300r/min, and the extrusion temperature is preferably 200-230 ℃;
(2) Placing the preparation raw materials of the inner layer structure resin into an internal mixer for internal mixing reaction and extrusion granulation to obtain the inner layer structure resin, wherein the internal mixer temperature is preferably 270-290 ℃, the internal mixing reaction time is 15-30min, and the rotating speed is 20-40 r/min;
(3) And plasticizing the outer layer structural resin and the inner layer structural resin, and preparing the polypropylene fiber material with the core layer and the skin layer through a sheath-core composite spinning process, wherein the spinning process temperature of the outer layer structural resin is preferably 200-230 ℃, and the spinning process temperature of the inner layer structural resin is preferably 270-290 ℃.
The third aspect of the invention provides an application of the polypropylene fiber material or the polypropylene fiber material prepared by the preparation method in concrete reinforcement.
The technical scheme provided by the invention has the following beneficial effects:
(1) The polypropylene fiber material has a specific double-layer structure, the outer layer structure resin uses the homopolymerized polypropylene, and the toughness of the homopolymerized polypropylene material can be improved by matching the nucleating agent (preferably beta nucleating agent) with the homopolymerized polypropylene; the calcium silicate whisker in the outer layer structural resin is easy to generate hydration reaction with concrete, so that the interfacial bonding capability of the polypropylene fiber material and the concrete is further improved. The ethylene acrylic acid copolymer and the calcium silicate whisker in the outer layer structural resin are used together, so that on one hand, the dispersion performance of the calcium silicate whisker in the polypropylene resin can be improved, and on the other hand, the ethylene acrylic acid copolymer and the homo-polypropylene are matched for use, so that the surface polarity of the polypropylene resin can be improved, and the interfacial bonding capability of the polypropylene fiber material and the concrete is improved;
(2) The polypropylene fiber material has a specific double-layer structure, the internal layer structure resin adopts polyethylene glycol terephthalate and glycidyl methacrylate grafted polypropylene to carry out banburying grafting reaction, and the carboxyl functional group of the polyethylene glycol terephthalate and the glycidyl methacrylate functional group carry out ring opening reaction, so that the compatibility and interface binding force of the internal layer resin and the external layer structure resin can be improved;
(3) The polypropylene fiber material has a specific double-layer structure, and the outer-layer structure resin coated by the outer layer has excellent concrete corrosion resistance, so that the problem that polyethylene terephthalate resin used by the inner-layer structure resin is easy to hydrolyze when meeting concrete can be solved, and the comprehensive mechanical property and the durability of the polypropylene fiber material in the concrete are improved.
Detailed Description
The invention will now be further illustrated by the following specific examples which are given by way of illustration only and are not intended to limit the scope of the invention thereto.
In the following examples, a method for preparing a polypropylene fiber material comprises the steps of:
(1) Putting the preparation raw materials of the outer layer structure resin into a double-screw extruder for melt dispersion and extrusion granulation to obtain the outer layer structure resin, wherein the length-diameter ratio of the screw of the double-screw extruder is (40-52): 1, the rotating speed of a screw is 100-300r/min, and the extrusion temperature is 200-230 ℃;
(2) Placing the preparation raw materials of the inner layer structure resin into an internal mixer for internal mixing reaction and extrusion granulation to obtain the inner layer structure resin, wherein the internal mixer has the temperature of 270-290 ℃, the internal mixing reaction time of 15-30min and the rotating speed of 20-40 r/min;
(3) And plasticizing the outer layer structural resin and the inner layer structural resin, and preparing the polypropylene fiber material with the core layer and the skin layer through a sheath-core composite spinning process, wherein the spinning process temperature of the outer layer structural resin is 200-230 ℃, and the spinning process temperature of the inner layer structural resin is 270-290 ℃.
The polypropylene fiber material comprises a core layer and a skin layer positioned at the periphery of the core layer, wherein the material of the skin layer is outer layer structural resin, and the material of the core layer is inner layer structural resin; the outer layer structural resin is prepared from preparation raw materials comprising homopolypropylene, ethylene acrylic acid copolymer, calcium silicate whisker and nucleating agent; the inner layer structure resin is prepared from preparation raw materials comprising polyethylene terephthalate and glycidyl methacrylate grafted polypropylene; the outer layer structural resin accounts for 20-50% of the total mass of the polypropylene fiber material, and the inner layer structural resin accounts for 50-80% of the total mass of the polypropylene fiber material.
In the preparation raw materials of the outer layer structural resin, the dosage of the homo-polypropylene is 75-88 parts by weight, the dosage of the ethylene acrylic acid copolymer is 5-10 parts by weight, the dosage of the calcium silicate whisker is 5-15 parts by weight, and the dosage of the nucleating agent is 0.1-0.5 part by weight; in the preparation raw materials of the inner layer structure resin, the dosage of polyethylene terephthalate is 79-89 parts by weight, and the dosage of glycidyl methacrylate grafted polypropylene is 10-20 parts by weight;
preferably, the preparation raw materials of the outer layer structural resin further comprise: antioxidants and lubricants; further preferably, in the raw materials for preparing the outer layer structural resin, the antioxidant and the lubricant are respectively 0.2-0.5 part by weight and 0.2-0.5 part by weight in sequence;
preferably, the preparation raw materials of the inner layer structure resin further comprise: antioxidants and lubricants; further preferably, in the raw materials for preparing the inner layer structural resin, the antioxidant and the lubricant are respectively 0.2-0.5 part by weight and 0.2-0.5 part by weight in sequence.
The melt index of the homo-polypropylene used for preparing the outer layer structural resin is 20-50 g/10min (230 ℃,2.16 kg).
The ethylene acrylic acid copolymer used for preparing the outer layer structural resin has a melt index of 5-20 g/10min (190 ℃,2.16 kg) and the mass content of acrylic acid is 5-22%.
The laser diffraction particle diameter D50 of the calcium silicate whisker used for preparing the outer layer structural resin is less than or equal to 7um; the nucleating agent used for preparing the outer layer structural resin is polypropylene beta nucleating agent.
The antioxidants used for preparing the outer layer structural resin comprise a main antioxidant and an auxiliary antioxidant, wherein the main antioxidant is one or more of hindered phenol antioxidants, such as 1010, 1076 of Li Anlong and 1330 of basf of Xinxiu chemistry; the auxiliary antioxidant is phosphite antioxidant and/or thioester antioxidant, such as one or more of 168 of Xinxiu chemical, DSTDP of Xinxiu chemical, 126 of Basoff, etc.; the mass ratio of the main antioxidant to the auxiliary antioxidant is 1: 1-2: 1, a step of; and/or the lubricant used for preparing the outer layer structure resin is any one or more of zinc stearate and ethylene bis-stearamide;
and/or the antioxidants used for preparing the inner layer structure resin comprise a main antioxidant and an auxiliary antioxidant, wherein the main antioxidant is one or more of hindered phenol antioxidants, such as 1010, 1076 of Li Anlong, 1330 of basf and the like of Xinxiu chemistry; the auxiliary antioxidant is phosphite antioxidant and/or thioester antioxidant, such as one or more of 168 of Xinxiu chemical, DSTDP of Xinxiu chemical, 126 of Basoff, etc.; the mass ratio of the main antioxidant to the auxiliary antioxidant is 1: 1-2: 1, a step of; and/or the lubricant used for preparing the inner layer structure resin is any one or more of zinc stearate and ethylene bis stearamide.
The polyethylene terephthalate used for preparing the inner layer structure resin has an intrinsic viscosity of 0.60-0.85 dL/g measured according to GB/T14190 and a carboxyl end group content of 20-30 mol/T measured according to FZ/T50012.
The melt index of the glycidyl methacrylate grafted polypropylene used for preparing the inner layer structure resin is 10-25 g/10min (190 ℃,2.16 kg), and the grafting rate of the glycidyl methacrylate is 0.5-2%.
The apparatus and reagents used in the examples or comparative examples:
Instrument:
twin screw extruder: model SK-26, screw aspect ratio of 50:1, a step of; nanjac chemical industry suite, inc.;
Single screw coextrusion apparatus: model HRJSJ-35, screw length-diameter ratio 28:1, sea Ruijia precision extrusion machinery Co., ltd;
Banbury mixer: model RX 5-10L, rui An Shiri New rubber and plastic machinery Co., ltd;
spinning testing machine: the model is FDY spinning tester, changzhou Ling fiber textile machinery Co.
Reagent:
homo-polypropylene: Z30S, melt index 26 g/10min (230 ℃,2.16 kg), china petrochemical Co., ltd;
Ethylene acrylic acid copolymer: EAA3004, acrylic acid content 9.7% by mass, melt index 8.5 g/10min (190 ℃,2.16 kg), SK Chemie Co Ltd;
calcium silicate whiskers: WFB5, laser diffraction particle size D50 4.9um, hubei Feng Gushan silicon fiber company;
beta nucleating agent: TMB-5 (aryl dimethylamide), all of the chemical industry research companies in Shanxi province;
and (3) a main antioxidant: 1010 (pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), chemistry;
auxiliary antioxidant: 168 (tris [2, 4-di-t-butylphenyl ] phosphite), neoxiu chemistry;
Polyethylene terephthalate: SD500, the intrinsic viscosity is 0.675 dL/g, and the carboxyl end group content is 24 mol/T;
Glycidyl methacrylate grafted polypropylene: SPG-02, melt index of 15 g/10min (190 ℃,2.16 kg), glycidyl methacrylate grafting of 1.2%;
The other raw materials are all commercial raw materials and are analytically pure.
The performance characterization method of the polypropylene fiber material prepared by the invention comprises the following steps:
The alkali-resistant tensile strength test method of the fiber comprises the following steps: the fibers were left to stand in an aqueous sodium hydroxide solution of ph=12 for 7d, and then taken out and dried for tensile property test.
The preparation process of the cement concrete comprises the following steps: adding 10kg of cement and 0.1kg of polypropylene fiber material into a stirrer, carrying out dry stirring for 5min, slowly adding 4kg of water, uniformly stirring for 10min, and taking out for subsequent experiments;
Casting the concrete by using a mould, and testing the compressive strength and the flexural strength according to the GB/T17671-2021 method after the cement is solidified for 28 days;
the fiber interface tensile strength testing method comprises the following steps: the polypropylene fiber is embedded into cement concrete for 10mm depth, after the cement is solidified for 24 hours, a monofilament pulling experiment is adopted, and the interfacial tensile strength of the fiber and the cement is measured according to the JT/T525-2004 method.
Spinnability evaluation: the spinning process is not broken, and the spinnability is judged to be good; and (5) yarn breakage occurs in the spinning process, and the spinnability is judged to be poor.
Tensile strength and elongation at break test criteria for fiber: GB/T3916-2013.
Example 1
The preparation method of the polypropylene fiber material comprises the following steps:
(1) 75 parts by weight of Z30S, 9.3 parts by weight of EAA3004, 15 parts by weight of WFB5, 0.1 part by weight of TMB-5, 0.2 part by weight of 1010, 0.2 part by weight of 168 and 0.2 part by weight of zinc stearate are added to a mixer and mixed for 3 minutes, and fed from a main feed port of a twin-screw extruder, the twin-screw extruder having a screw aspect ratio of 50:1, extruding at 220 ℃ at the screw rotating speed of 300r/min, and obtaining outer layer structural resin through melt dispersion and extrusion granulation;
(2) 79 parts by weight of SD500, 20 parts by weight of SPG-02, 0.25 part by weight of 1010, 0.25 part by weight of 168 and 0.5 part by weight of zinc stearate are added into a mixer, mixed for 3min, placed into an internal mixer for banburying reaction, wherein the banburying temperature is 280 ℃, the banburying reaction time is 15min, the rotating speed is 30 r/min, and extrusion granulation is carried out to obtain the internal layer structure resin;
(3) Respectively placing the outer layer structural resin and the inner layer structural resin into two single screw extruders for plasticizing, then entering a spinning test machine, wherein the spinning process temperature of the outer layer structural resin is 220 ℃, the spinning process temperature of the inner layer structural resin is 280 ℃, and preparing the polypropylene fiber material through a sheath-core composite spinning process.
The outer layer structure resin accounts for 20% of the total mass of the polypropylene fiber material, and the inner layer structure resin accounts for 80% of the total mass of the polypropylene fiber material.
Properties of the polypropylene fiber material prepared in example 1: the polypropylene fiber material has good fiber spinnability; the tensile strength of the fiber is 980Mpa, the tensile elongation at break of the fiber is 46%, the alkali resistance tensile strength of the fiber is 970Mpa, the interfacial tensile strength of the fiber is 0.32Mpa, the compressive strength of the concrete is 85Mpa, and the flexural strength of the concrete is 12Mpa.
Example 2
The preparation method of the polypropylene fiber material comprises the following steps:
(1) 75 parts by weight of Z30S, 10 parts by weight of EAA3004, 14.3 parts by weight of WFB5, 0.1 part by weight of TMB-5, 0.2 part by weight of 1010, 0.2 part by weight of 168 and 0.2 part by weight of zinc stearate are added to a mixer and mixed for 3 minutes, and fed from a main feed port of a twin-screw extruder, the twin-screw extruder having a screw aspect ratio of 50:1, extruding at 220 ℃ at the screw rotating speed of 300r/min, and obtaining outer layer structural resin through melt dispersion and extrusion granulation;
(2) 79 parts by weight of SD500, 20 parts by weight of SPG-02, 0.25 part by weight of 1010, 0.25 part by weight of 168 and 0.5 part by weight of zinc stearate are added into a mixer, mixed for 3min, placed into an internal mixer for banburying reaction, wherein the banburying temperature is 280 ℃, the banburying reaction time is 15min, the rotating speed is 30 r/min, and extrusion granulation is carried out to obtain the internal layer structure resin;
(3) Respectively placing the outer layer structural resin and the inner layer structural resin into two single screw extruders for plasticizing, then entering a spinning test machine, wherein the spinning process temperature of the outer layer structural resin is 220 ℃, the spinning process temperature of the inner layer structural resin is 280 ℃, and preparing the polypropylene fiber material through a sheath-core composite spinning process.
The outer layer structure resin accounts for 35% of the total mass of the polypropylene fiber material, and the inner layer structure resin accounts for 65% of the total mass of the polypropylene fiber material.
Properties of the polypropylene fiber material prepared in example 2: the polypropylene fiber material has good fiber spinnability; the tensile strength of the fiber is 930Mpa, the tensile elongation at break of the fiber is 51%, the alkali resistance tensile strength of the fiber is 928Mpa, the tensile strength of the fiber interface is 0.31Mpa, the compressive strength of the concrete is 83Mpa, and the flexural strength of the concrete is 11Mpa.
Example 3
The preparation method of the polypropylene fiber material comprises the following steps:
(1) 80 parts by weight of Z30S, 8.7 parts by weight of EAA3004, 10 parts by weight of WFB5, 0.3 part by weight of TMB-5, 0.25 part by weight of 1010, 0.25 part by weight of 168 and 0.5 part by weight of zinc stearate are added to a mixer and mixed for 3 minutes, and fed from a main feed port of a twin-screw extruder having a screw aspect ratio of 50:1, extruding at 220 ℃ at the screw rotating speed of 300r/min, and obtaining outer layer structural resin through melt dispersion and extrusion granulation;
(2) 79 parts by weight of SD500, 20 parts by weight of SPG-02, 0.25 part by weight of 1010, 0.25 part by weight of 168 and 0.5 part by weight of zinc stearate are added into a mixer, mixed for 3min, placed into an internal mixer for banburying reaction, wherein the banburying temperature is 280 ℃, the banburying reaction time is 15min, the rotating speed is 30 r/min, and extrusion granulation is carried out to obtain the internal layer structure resin;
(3) Respectively placing the outer layer structural resin and the inner layer structural resin into two single screw extruders for plasticizing, then entering a spinning test machine, wherein the spinning process temperature of the outer layer structural resin is 220 ℃, the spinning process temperature of the inner layer structural resin is 280 ℃, and preparing the polypropylene fiber material through a sheath-core composite spinning process.
The outer layer structure resin accounts for 50% of the total mass of the polypropylene fiber material, and the inner layer structure resin accounts for 50% of the total mass of the polypropylene fiber material.
Properties of the polypropylene fiber material prepared in example 3: the polypropylene fiber material has good fiber spinnability; the tensile strength of the fiber is 900Mpa, the tensile elongation at break of the fiber is 55%, the alkali resistance tensile strength of the fiber is 880Mpa, the tensile strength of the fiber interface is 0.29Mpa, the compressive strength of the concrete is 79Mpa, and the flexural strength of the concrete is 9.9Mpa.
Example 4
The preparation method of the polypropylene fiber material comprises the following steps:
(1) 88 parts by weight of Z30S, 5 parts by weight of EAA3004, 5.5 parts by weight of WFB5, 0.5 part by weight of TMB-5, 0.25 part by weight of 1010, 0.25 part by weight of 168 and 0.5 part by weight of zinc stearate are added to a mixer and mixed for 3 minutes, and fed from a main feed port of a twin-screw extruder having a screw aspect ratio of 50:1, extruding at 220 ℃ at the screw rotating speed of 300r/min, and obtaining outer layer structural resin through melt dispersion and extrusion granulation;
(2) Adding 84 parts by weight of SD500, 15 parts by weight of SPG-02, 0.25 part by weight of 1010, 0.25 part by weight of 168 and 0.5 part by weight of zinc stearate into a mixer, mixing for 3min, placing into an internal mixer for banburying reaction at 280 ℃ for 15min at a rotating speed of 30 r/min, extruding and granulating to obtain inner layer structural resin;
(3) Respectively placing the outer layer structural resin and the inner layer structural resin into two single screw extruders for plasticizing, then entering a spinning test machine, wherein the spinning process temperature of the outer layer structural resin is 220 ℃, the spinning process temperature of the inner layer structural resin is 280 ℃, and preparing the polypropylene fiber material through a sheath-core composite spinning process.
The outer layer structure resin accounts for 20% of the total mass of the polypropylene fiber material, and the inner layer structure resin accounts for 80% of the total mass of the polypropylene fiber material.
Properties of the polypropylene fiber material prepared in example 4: the polypropylene fiber material has good fiber spinnability; the tensile strength of the fiber is 1030Mpa, the tensile elongation at break of the fiber is 48%, the alkali resistance tensile strength of the fiber is 1009Mpa, the interfacial tensile strength of the fiber is 0.27Mpa, the compressive strength of the concrete is 87Mpa, and the flexural strength of the concrete is 13Mpa.
Example 5
The preparation method of the polypropylene fiber material comprises the following steps:
(1) 88 parts by weight of Z30S, 5.5 parts by weight of EAA3004, 5 parts by weight of WFB5, 0.5 part by weight of TMB-5, 0.25 part by weight of 1010, 0.25 part by weight of 168 and 0.5 part by weight of zinc stearate are added to a mixer and mixed for 3 minutes, fed from a main feed port of a twin-screw extruder having a screw aspect ratio of 50:1, extruding at 220 ℃ at the screw rotating speed of 300r/min, and obtaining outer layer structural resin through melt dispersion and extrusion granulation;
(2) 89 parts by weight of SD500, 10 parts by weight of SPG-02, 0.25 part by weight of 1010, 0.25 part by weight of 168 and 0.5 part by weight of zinc stearate are added into a mixer, mixed for 3min, placed into an internal mixer for banburying reaction, wherein the banburying temperature is 280 ℃, the banburying reaction time is 15min, the rotating speed is 30 r/min, and extrusion granulation is carried out to obtain the internal layer structure resin;
(3) Respectively placing the outer layer structural resin and the inner layer structural resin into two single screw extruders for plasticizing, then entering a spinning test machine, wherein the spinning process temperature of the outer layer structural resin is 220 ℃, the spinning process temperature of the inner layer structural resin is 280 ℃, and preparing the polypropylene fiber material through a sheath-core composite spinning process.
The outer layer structure resin accounts for 20% of the total mass of the polypropylene fiber material, and the inner layer structure resin accounts for 80% of the total mass of the polypropylene fiber material.
Properties of the polypropylene fiber material prepared in example 5: the polypropylene fiber material has good fiber spinnability; the tensile strength of the fiber is 1010Mpa, the tensile elongation at break of the fiber is 47%, the alkali resistance tensile strength of the fiber is 998Mpa, the interfacial tensile strength of the fiber is 0.28Mpa, the compressive strength of the concrete is 86Mpa, and the flexural strength of the concrete is 12.7Mpa.
The polypropylene fiber materials in the embodiments 1 to 5 of the invention are all of double-layer structures, and the homo-polypropylene and the beta nucleating agent are matched in the raw materials for preparing the outer layer structure resin, so that the toughness of the material can be improved, and the tensile elongation at break of the polypropylene fiber material is higher. And calcium silicate whisker is added into the raw materials for preparing the outer layer structural resin to carry out hydration reaction with concrete, so that the interfacial tensile strength of the polypropylene fiber material and the concrete is further improved. The ethylene acrylic acid copolymer is added, so that on one hand, the dispersion performance of the calcium silicate whisker in the polypropylene resin can be improved by the synergistic effect of the ethylene acrylic acid copolymer and the calcium silicate whisker, the fiber spinnability is better, and on the other hand, the surface polarity of the polypropylene resin can be improved by the synergistic effect of the ethylene acrylic acid copolymer and the homo-polypropylene, and the interfacial tensile strength of the polypropylene fiber material and the concrete is improved. In the preparation of the raw materials of the inner-layer structural resin, the polyethylene terephthalate and the glycidyl methacrylate grafted polypropylene are used for carrying out banburying grafting reaction together, and the carboxyl functional group of the polyethylene terephthalate and the glycidyl ester functional group are subjected to ring opening reaction, so that the compatibility and interfacial binding force of the inner-layer structural resin and the outer-layer structural resin can be improved, the high-strength performance of the inner-layer structural resin can be fully exerted by the polypropylene fiber material, and the prepared concrete material has higher compressive strength and flexural strength. The outer layer structure resin coated by the outer layer has excellent concrete corrosion resistance, and can solve the problem that the inner layer polyethylene terephthalate resin is easy to hydrolyze when meeting concrete, thereby improving the alkali resistance tensile strength of the polypropylene fiber material.
Comparative example 1
The difference between comparative example 1 and example 1 is that: the ethylene acrylic acid copolymer is not added into the raw material for preparing the outer layer structural resin.
Properties of the polypropylene fiber material prepared in comparative example 1: the spinnability of the polypropylene fiber material is poor; the tensile strength of the fiber is 920Mpa, the tensile elongation at break of the fiber is 21%, the alkali resistance tensile strength of the fiber is 890Mpa, the tensile strength of the fiber interface is 0.11Mpa, the compressive strength of the concrete is 70Mpa, and the flexural strength of the concrete is 8.1Mpa.
In comparative example 1, no ethylene acrylic acid copolymer was added to the raw material for preparing the outer layer structural resin, the dispersibility of the calcium silicate whisker in polypropylene was poor, the spinnability of the obtained material was poor, the tensile elongation at break was low, and the bonding capacity of the interface of the obtained material and concrete was reduced, and the tensile strength, compressive strength and flexural strength of the concrete material were reduced.
Comparative example 2
The difference between comparative example 2 and example 1 is that: no calcium silicate whisker is added into the raw materials for preparing the outer layer structural resin.
Properties of the polypropylene fiber material prepared in comparative example 2: the spinnability of the polypropylene fiber material is good; the tensile strength of the fiber is 910Mpa, the tensile elongation at break of the fiber is 45%, the alkali resistance tensile strength of the fiber is 897Mpa, the tensile strength of the fiber interface is 0.10Mpa, the compressive strength of the concrete is 69Mpa, and the flexural strength of the concrete is 7.8Mpa.
In comparative example 2, calcium silicate whiskers are not added to the raw material for preparing the outer layer structural resin, so that the bonding capability of the interface between the obtained material and concrete is reduced, and the tensile strength, compressive strength and flexural strength of the concrete material are reduced.
Comparative example 3
The difference between comparative example 3 and example 1 is that: the beta nucleating agent is not added into the raw materials for preparing the outer layer structural resin.
Properties of the polypropylene fiber material prepared in comparative example 3: the spinnability of the polypropylene fiber material is good; the tensile strength of the fiber is 970Mpa, the tensile elongation at break of the fiber is 19%, the alkali resistance tensile strength of the fiber is 955Mpa, the interfacial tensile strength of the fiber is 0.22Mpa, the compressive strength of the concrete is 75Mpa, and the flexural strength of the concrete is 8.3Mpa.
In comparative example 3, the material obtained by adding no β nucleating agent to the raw material for preparing the outer layer structural resin has a low elongation at break, and is easily broken by external force, thereby reducing the compressive strength and flexural strength of the concrete material.
Comparative example 4
Comparative example 4 differs from example 1 in that: the glycidyl methacrylate grafted polypropylene is not added into the raw materials for preparing the inner layer structure resin.
Properties of the polypropylene fiber material prepared in comparative example 4: the spinnability of the polypropylene fiber material is poor; the tensile strength of the fiber is 880Mpa, the tensile elongation at break of the fiber is 18%, the alkali resistance tensile strength of the fiber is 855Mpa, the interfacial tensile strength of the fiber is 0.21Mpa, the compressive strength of the concrete is 72Mpa, and the flexural strength of the concrete is 7.6Mpa.
In comparative example 4, glycidyl methacrylate grafted polypropylene is not added into the raw material for preparing the inner layer structural resin, the compatibility and interface bonding property of the outer layer structural resin and the inner layer structural resin of the obtained material are poor, the problems of poor coating property and poor spinnability easily occur in the spinning process, the skin-core separation phenomenon easily occurs when the obtained material is subjected to external force, the high-strength performance of the inner layer structural resin cannot be fully exerted, and the compressive strength and the flexural strength of the concrete material are reduced.
Comparative example 5
Comparative example 5 differs from example 1 in that: the prepared polypropylene fiber material is not of a double-layer structure, and only has outer-layer structural resin.
Properties of the polypropylene fiber material prepared in comparative example 5: the spinnability of the polypropylene fiber material is good; the tensile strength of the fiber is 610Mpa, the tensile elongation at break of the fiber is 47%, the alkali resistance tensile strength of the fiber is 598Mpa, the tensile strength of the fiber interface is 0.28Mpa, the compressive strength of the concrete is 53Mpa, and the flexural strength of the concrete is 5.8Mpa.
In comparative example 5, the prepared polypropylene fiber material is not of a double-layer structure, only has outer-layer structural resin, and the obtained material has lower tensile strength, and reduces the compressive strength and the flexural strength of the concrete material.
Comparative example 6
Comparative example 6 differs from example 1 in that: the prepared polypropylene fiber material is not of a double-layer structure, and only has inner-layer structure resin.
Properties of the polypropylene fiber material prepared in comparative example 6: the spinnability of the polypropylene fiber material is good; the tensile strength of the fiber is 990Mpa, the tensile elongation at break of the fiber is 30%, the alkali resistance tensile strength of the fiber is 530Mpa, the tensile strength of the fiber interface is 0.29Mpa, the compressive strength of the concrete is 47Mpa, and the flexural strength of the concrete is 5.2Mpa.
In comparative example 6, the prepared polypropylene fiber material is not of a double-layer structure, only has an inner-layer structure resin, has no coating protection effect of an outer-layer structure resin, and the polyethylene terephthalate resin is easy to hydrolyze in a concrete high-alkaline environment, so that the alkali-resistant tensile strength of the polyethylene terephthalate resin is lower, and the compressive strength and the flexural strength of the concrete material are reduced.
Comparative example 7
Comparative example 7 differs from example 1 in that the parts by weight of the raw materials are different: the outer layer structural resin is prepared by adopting 93.35 parts by weight of Z30S, 3 parts by weight of EAA3004, 3 parts by weight of WFB5 and 0.05 part by weight of TMB-5; 94 parts by weight of SD500 and 5 parts by weight of SPG-02 were used for preparing the inner layer structure resin.
Properties of the polypropylene fiber material prepared in comparative example 7: the spinnability of the polypropylene fiber material is good; the tensile strength of the fiber is 880Mpa, the tensile elongation at break of the fiber is 25%, the alkali resistance tensile strength of the fiber is 910Mpa, the tensile strength of the fiber interface is 0.12Mpa, the compressive strength of the concrete is 78Mpa, and the flexural strength of the concrete is 9.5Mpa.
In comparative example 7, the ethylene acrylic acid copolymer, calcium silicate whisker and beta nucleating agent are low in content, the obtained material cannot form a better beta crystal form, the toughness is reduced, the elongation at break is low, meanwhile, fewer calcium silicate whisker and concrete are subjected to hydration reaction, and the interfacial bonding capability of the obtained material and concrete is reduced; the content of the glycidyl methacrylate grafted polypropylene in the inner layer is low, the compatibility of the inner layer resin and the outer layer resin of the obtained material is reduced, and the tensile strength of the material is low, and the compressive and flexural strength of the concrete is low.
TABLE 1 Properties of Polypropylene fiber materials prepared in examples 1-5 and comparative examples 1-7
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (10)
1. A polypropylene fiber material characterized by: the polypropylene fiber material comprises a core layer and a skin layer positioned at the periphery of the core layer, wherein the skin layer is made of outer-layer structural resin, and the core layer is made of inner-layer structural resin;
The outer layer structural resin is prepared from preparation raw materials comprising homopolypropylene, ethylene acrylic acid copolymer, calcium silicate whisker and nucleating agent;
the inner layer structure resin is prepared from preparation raw materials comprising polyethylene terephthalate and glycidyl methacrylate grafted polypropylene;
the outer layer structural resin accounts for 20-50% of the total mass of the polypropylene fiber material, and the inner layer structural resin accounts for 50-80% of the total mass of the polypropylene fiber material.
2. The polypropylene fiber material according to claim 1, wherein: in the preparation raw materials of the outer layer structural resin, the dosage of the homo-polypropylene is 75-88 parts by weight, the dosage of the ethylene acrylic acid copolymer is 5-10 parts by weight, the dosage of the calcium silicate whisker is 5-15 parts by weight, and the dosage of the nucleating agent is 0.1-0.5 part by weight; in the preparation raw materials of the inner layer structure resin, the dosage of polyethylene terephthalate is 79-89 parts by weight, and the dosage of glycidyl methacrylate grafted polypropylene is 10-20 parts by weight;
preferably, the preparation raw materials of the outer layer structural resin further comprise: antioxidants and lubricants; further preferably, in the raw materials for preparing the outer layer structural resin, the antioxidant and the lubricant are respectively 0.2-0.5 part by weight and 0.2-0.5 part by weight in sequence;
preferably, the preparation raw materials of the inner layer structure resin further comprise: antioxidants and lubricants; further preferably, in the raw materials for preparing the inner layer structural resin, the antioxidant and the lubricant are respectively 0.2-0.5 part by weight and 0.2-0.5 part by weight in sequence.
3. The polypropylene fiber material according to claim 1 or 2, wherein the melt index of the homo-polypropylene used for preparing the outer structural resin is 20-50 g/10min (230 ℃,2.16 kg).
4. The polypropylene fiber material according to claim 1 or 2, wherein the ethylene acrylic acid copolymer used for preparing the outer structural resin has a melt index of 5 to 20 g/10min (190 ℃,2.16 kg) and a mass content of acrylic acid of 5 to 22%.
5. The polypropylene fiber material according to claim 1 or 2, wherein the calcium silicate whisker used for preparing the outer layer structural resin has a laser diffraction particle diameter d50 less than or equal to 7um;
the nucleating agent used for preparing the outer layer structural resin is polypropylene beta nucleating agent.
6. The polypropylene fiber material according to claim 2, wherein the antioxidants used for preparing the outer layer structural resin comprise a main antioxidant and an auxiliary antioxidant, and the main antioxidant is a hindered phenol antioxidant; the auxiliary antioxidant is phosphite antioxidant and/or thioester antioxidant; the mass ratio of the main antioxidant to the auxiliary antioxidant is 1: 1-2: 1, a step of;
And/or the lubricant used for preparing the outer layer structure resin is any one or more of zinc stearate and ethylene bis-stearamide;
And/or the antioxidant used for preparing the inner layer structure resin comprises a main antioxidant and an auxiliary antioxidant, wherein the main antioxidant is a hindered phenol antioxidant; the auxiliary antioxidant is phosphite antioxidant and/or thioester antioxidant; the mass ratio of the main antioxidant to the auxiliary antioxidant is 1: 1-2: 1, a step of;
and/or the lubricant used for preparing the inner layer structure resin is any one or more of zinc stearate and ethylene bis stearamide.
7. The polypropylene fiber material according to claim 1, wherein the polyethylene terephthalate used for the preparation of the inner structural resin has an intrinsic viscosity of 0.60 to 0.85 dL/g as measured according to GB/T14190 and a carboxyl end group content of 20 to 30 mol/T as measured according to FZ/T50012.
8. The polypropylene fiber material according to claim 1, wherein the glycidyl methacrylate grafted polypropylene used for preparing the inner layer structural resin has a melt index of 10-25 g/10min (190 ℃,2.16 kg) and a glycidyl methacrylate grafting ratio of 0.5-2%.
9. A method for preparing a polypropylene fiber material according to any one of claims 1 to 8, comprising the steps of:
(1) The preparation raw materials of the outer layer structure resin are placed in a double-screw extruder for melt dispersion and extrusion granulation to obtain the outer layer structure resin, and the length-diameter ratio of the screw of the double-screw extruder is preferably (40-52): 1, the rotating speed of the screw is 100-300r/min, and the extrusion temperature is preferably 200-230 ℃;
(2) Placing the preparation raw materials of the inner layer structure resin into an internal mixer for internal mixing reaction and extrusion granulation to obtain the inner layer structure resin, wherein the internal mixer temperature is preferably 270-290 ℃, the internal mixing reaction time is 15-30min, and the rotating speed is 20-40 r/min;
(3) And plasticizing the outer layer structural resin and the inner layer structural resin, and preparing the polypropylene fiber material with the core layer and the skin layer through a sheath-core composite spinning process, wherein the spinning process temperature of the outer layer structural resin is preferably 200-230 ℃, and the spinning process temperature of the inner layer structural resin is preferably 270-290 ℃.
10. Use of the polypropylene fiber material of any one of claims 1 to 8 or the polypropylene fiber material produced by the production method of claim 9 in concrete reinforcement.
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| CN105733093A (en) * | 2016-03-28 | 2016-07-06 | 中国石油化工股份有限公司 | Special high-flowability resin for polypropylene fibers and preparation method thereof |
| CN111718538A (en) * | 2019-03-19 | 2020-09-29 | 中国石化扬子石油化工有限公司 | High-rigidity high-impact-resistance polypropylene resin composition and preparation method thereof |
| CN117865603A (en) * | 2023-12-29 | 2024-04-12 | 中铁十一局集团桥梁有限公司 | Concrete and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105733093A (en) * | 2016-03-28 | 2016-07-06 | 中国石油化工股份有限公司 | Special high-flowability resin for polypropylene fibers and preparation method thereof |
| CN111718538A (en) * | 2019-03-19 | 2020-09-29 | 中国石化扬子石油化工有限公司 | High-rigidity high-impact-resistance polypropylene resin composition and preparation method thereof |
| CN117865603A (en) * | 2023-12-29 | 2024-04-12 | 中铁十一局集团桥梁有限公司 | Concrete and preparation method thereof |
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