Disclosure of Invention
The invention mainly aims to provide the non-woven fabric for the photovoltaic table paper, which has the advantages of good mechanical property, good air permeability and smoothness, and excellent thermal stability and aging resistance, and the preparation process thereof.
In order to achieve the purpose, the invention provides a non-woven fabric for photovoltaic table paper, which is prepared from the following raw materials in parts by weight: 50-60 parts of PET (polyethylene terephthalate) polyester chip, 10-20 parts of carboxyl-terminated hyperbranched polyester, 4, 8-tricyclo [5.2.1.O2,7] decane dimethanol ester, 15-25 parts of poly (2, 3,5, 6-tetrafluoroterephthalic acid), 0.8-1.5 parts of coupling agent, 0.5-1 part of antioxidant, 1-3 parts of plasticizer, 5-8 parts of filler, 2-4 parts of aziridine crosslinking agent and 0.5-1.5 parts of chitosan quaternary ammonium salt.
Preferably, the PET polyester chip is a bright polyester chip BRN-24 produced by China petrochemical industry.
Preferably, the source of the carboxyl-terminated hyperbranched polyester is not particularly required, and in one embodiment of the invention, the carboxyl-terminated hyperbranched polyester is at least one of HyPer C403 and HyPer C404 manufactured by wuhan hyperbranched resin technologies.
Preferably, the preparation method of the poly (2, 3,5, 6-tetrafluoroterephthalic acid) 4, 8-tricyclo [5.2.1.O2,7] decane dimethanol ester comprises the following steps: adding 2,3,5, 6-tetrafluoroterephthalic acid, 4, 8-tricyclo [5.2.1.O2,7] decanedimethanol, dicyclohexylcarbodiimide DCC, 4-dimethylaminopyridine DMAP and a catalyst into a high boiling point solvent, stirring uniformly, transferring the mixture into a high pressure reaction kettle, replacing air in the kettle by inert gas, carrying out esterification reaction at 100-120 ℃ for 4-6 hours, and fractionating water while reacting to obtain an oligomer; then carrying out polycondensation reaction for 4-6 hours under the conditions of reaction pressure of 30-80KPa and 235-250 ℃, after the reaction is finished, adjusting normal pressure and normal temperature, settling in water, washing the settled polymer with ethanol for 3-6 times, and finally drying the polymer in a vacuum drying oven at 85-95 ℃ to constant weight to obtain the 2,3,5, 6-tetrafluoroterephthalic acid 4, 8-tricyclo [5.2.1.O2,7] decane dimethanol ester.
Preferably, the mol ratio of the 2,3,5, 6-tetrafluoroterephthalic acid, the 4, 8-tricyclo [5.2.1.O2,7] decane dimethanol, dicyclohexylcarbodiimide DCC, 4-dimethylaminopyridine DMAP, the catalyst and the high boiling point solvent is 1:1 (0.6-1): 0.5 (0.3-0.5): 6-10.
Preferably, the catalyst is a mixture formed by mixing tetrabutyl titanate and tetraisopropyl titanate according to the mass ratio of 1 (0.8-1.2).
Preferably, the high boiling point solvent is dimethyl sulfoxide; the inert gas is any one of nitrogen, helium and neon.
Preferably, the coupling agent is at least one of a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH570; the antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant 1098 and antioxidant 168; the plasticizer is epoxidized soybean oil; the filler is calcium carbonate, and the particle size of the filler is 800-1000 meshes.
Preferably, the aziridine crosslinking agent is an aziridine crosslinking agent XR-100; the molecular weight of the chitosan quaternary ammonium salt is 10 ten thousand, the substitution degree is 90%, and the chitosan quaternary ammonium salt is provided by Shanghai source leaf biotechnology Co Ltd, and the product number is S26618-500g.
The invention also aims at providing a preparation process of the non-woven fabric for the photovoltaic table-board paper, which comprises the following steps of: uniformly mixing PET polyester chips, carboxyl-terminated hyperbranched polyester, poly (2, 3,5, 6-tetrafluoroterephthalic acid) 4, 8-tricyclo [5.2.1.O2,7] decane dimethanol ester, a coupling agent, an antioxidant, a plasticizer and a filler according to parts by weight to obtain a mixed material, adding the mixed material into a double-screw extruder, sequentially carrying out melt blowing, net forming, rolling into cloth by a rolling mill, soaking the modified liquid, drying and solidifying, washing by clear water, and drying to obtain the non-woven fabric for the photovoltaic mesa paper.
Preferably, the temperature of the rolling mill during rolling is 120-160 ℃, and the speed of the non-woven fabric passing through the hot roller of the rolling mill is 180-300 rpm.
Preferably, the modifying liquid is a mixed liquid of an aziridine crosslinking agent and chitosan quaternary ammonium salt; wherein the mass of the solvent water is 70-80wt% of the total mass of the mixed solution.
Preferably, the temperature of the drying and curing is 60-80 ℃ and the time is 2-4 hours.
Due to the application of the technical scheme, the invention has the following beneficial effects:
(1) The preparation process of the non-woven fabric for the photovoltaic mesa paper disclosed by the invention can be realized by adopting conventional equipment, has low energy consumption, less investment and high preparation efficiency and finished product qualification rate, and is suitable for continuous large-scale production.
(2) The invention discloses a non-woven fabric for photovoltaic table paper, which is prepared from the following raw materials in parts by weight: 50-60 parts of PET (polyethylene terephthalate) polyester chip, 10-20 parts of carboxyl-terminated hyperbranched polyester, 4, 8-tricyclo [5.2.1.O2,7] decane dimethanol ester, 15-25 parts of poly (2, 3,5, 6-tetrafluoroterephthalic acid), 0.8-1.5 parts of coupling agent, 0.5-1 part of antioxidant, 1-3 parts of plasticizer, 5-8 parts of filler, 2-4 parts of aziridine crosslinking agent and 0.5-1.5 parts of chitosan quaternary ammonium salt. Through the mutual cooperation and coaction of the raw materials, the prepared non-woven fabric has good mechanical properties, good air permeability and smoothness, and excellent thermal stability and aging resistance.
(3) The non-woven fabric for the photovoltaic table paper disclosed by the invention takes PET polyester chips as a base material, and carboxyl-terminated hyperbranched polyester and poly (2, 3,5, 6-tetrafluoroterephthalic acid) 4, 8-tricyclo [5.2.1.O2,7] decane dimethanol ester are added into the base material in a blending way, so that the advantages of the materials are combined, and the final non-woven fabric has the advantages of high tensile strength, low heat shrinkage, good heat stability, smooth and clean surface and good ageing resistance; the materials all contain aromatic polyester structures, so that the materials have good compatibility and performance stability; the 2,3,5, 6-tetrafluoroterephthalic acid 4, 8-tricyclo [5.2.1.O2,7] decane dimethanol ester is formed by the end-to-end esterification polycondensation reaction of 2,3,5, 6-tetrafluoroterephthalic acid and 4, 8-tricyclo [5.2.1.O2,7] decane dimethanol, and a tricycloalkane and tetrafluorobenzene structure is simultaneously introduced into a polymer molecular chain to be matched with other structures and groups, so that the ageing resistance, the smoothness and the mechanical properties of the prepared material are further improved under the multiple actions of an electronic effect, a steric effect and a conjugation effect.
(4) According to the non-woven fabric for the photovoltaic mesa paper, carboxyl on carboxyl-terminated hyperbranched polyester can respectively react with an aziridine crosslinking agent and chitosan quaternary ammonium salt to form a surface interpenetrating network crosslinking structure, so that the ageing resistance and the heat resistance of the material are further improved, and the performance stability of the material is higher. The modified liquid is soaked in the non-woven fabric surface to modify, so that uneven areas on the surface can be filled, smoothness is further improved, and the formed cross-linked structure can effectively prolong the service life of the material.
Detailed Description
The following description is presented to enable one of ordinary skill in the art to make and use the invention. The preferred embodiments in the following description are by way of example only and other obvious variations will occur to those skilled in the art.
Example 1
The non-woven fabric for the photovoltaic table-board paper is prepared from the following raw materials in parts by weight: 50 parts of PET polyester chip, 10 parts of carboxyl-terminated hyperbranched polyester, 15 parts of poly (2, 3,5, 6-tetrafluoroterephthalic acid) 4, 8-tricyclo [5.2.1.O2,7] decane dimethanol ester, 0.8 part of coupling agent, 0.5 part of antioxidant, 1 part of plasticizer, 5 parts of filler, 2 parts of aziridine crosslinking agent and 0.5 part of chitosan quaternary ammonium salt.
The PET polyester chip is a bright polyester chip BRN-24 produced by China petrochemical industry; the carboxyl-terminated hyperbranched polyester is HyPer C403 produced by Wuhan hyperbranched resin technology Co.
The poly (2, 3,5, 6-tetrafluoroterephthalic acid) 4, 8-tricyclo [5.2.1.O2,7]The preparation method of decane dimethanol ester comprises the following steps: 2,3,5, 6-tetrafluoroterephthalic acid, 4, 8-tricyclo [5.2.1.O2,7]Adding decanedimethanol, dicyclohexylcarbodiimide DCC, 4-dimethylaminopyridine DMAP and a catalyst into a high boiling point solvent, uniformly stirring, transferring into a high-pressure reaction kettle, and using inert gasThe gas replaces the air in the kettle, the esterification reaction is carried out for 4 hours at the temperature of 100 ℃, and water is fractionated while the reaction is carried out, so that the oligomer is obtained; then carrying out polycondensation reaction for 4 hours under the condition of reaction pressure of 30KPa and 235 ℃, after the reaction is finished, adjusting normal pressure and normal temperature, settling in water, washing the settled polymer with ethanol for 3 times, and finally drying the polymer in a vacuum drying oven at 85 ℃ to constant weight to obtain 2,3,5, 6-tetrafluoroterephthalic acid 4, 8-tricyclo [5.2.1.O2,7]]Decane dimethanol ester; the 2,3,5, 6-tetrafluoroterephthalic acid, 4, 8-tricyclo [5.2.1.O2,7]The molar ratio of decane dimethanol, dicyclohexylcarbodiimide DCC, 4-dimethylaminopyridine DMAP, catalyst and high boiling point solvent is 1:1:0.6:0.5:0.3:6; the catalyst is a mixture formed by mixing tetrabutyl titanate and tetraisopropyl titanate according to the mass ratio of 1:0.8; the high boiling point solvent is dimethyl sulfoxide; the inert gas is nitrogen. M of the Polymer by GPC testn =14620g/mol，MW /Mn =1.338。
The coupling agent is a silane coupling agent KH550; the antioxidant is antioxidant 1010; the plasticizer is epoxidized soybean oil; the filler is calcium carbonate, and the particle size of the filler is 800 meshes; the aziridine crosslinking agent is an aziridine crosslinking agent XR-100; the molecular weight of the chitosan quaternary ammonium salt is 10 ten thousand, the substitution degree is 90%, and the chitosan quaternary ammonium salt is provided by Shanghai source leaf biotechnology Co Ltd, and the product number is S26618-500g.
A preparation process of non-woven fabric for photovoltaic table-board paper comprises the following steps: uniformly mixing PET polyester chips, carboxyl-terminated hyperbranched polyesters, poly (2, 3,5, 6-tetrafluoroterephthalic acid) 4, 8-tricyclo [5.2.1.O2,7] decane dimethanol ester, a coupling agent, an antioxidant, a plasticizer and a filler according to parts by weight to obtain a mixed material, adding the mixed material into a double-screw extruder, sequentially carrying out melt blowing, net forming, rolling into cloth by a rolling mill, soaking the modified liquid, drying and solidifying, washing by clear water, and drying to prepare non-woven fabrics for photovoltaic mesa paper; the temperature of the rolling mill during rolling is 120 ℃, and the speed of the non-woven fabric passing through the hot roller of the rolling mill is 180 revolutions per minute; the modified liquid is a mixed liquid of an aziridine crosslinking agent and chitosan quaternary ammonium salt; wherein the mass of the solvent water is 70wt% of the total mass of the mixed solution; the drying and curing temperature is 60 ℃ and the time is 2 hours.
Example 2
The non-woven fabric for the photovoltaic table-board paper is prepared from the following raw materials in parts by weight: 52 parts of PET polyester chip, 12 parts of carboxyl-terminated hyperbranched polyester, 17 parts of poly (2, 3,5, 6-tetrafluoroterephthalic acid) 4, 8-tricyclo [5.2.1.O2,7] decane dimethanol ester, 1 part of coupling agent, 0.6 part of antioxidant, 1.5 parts of plasticizer, 6 parts of filler, 2.5 parts of aziridine crosslinking agent and 0.7 part of chitosan quaternary ammonium salt.
The PET polyester chip is a bright polyester chip BRN-24 produced by China petrochemical industry; the carboxyl-terminated hyperbranched polyester is HyPer C404 produced by Wuhan hyperbranched resin technology Co.
The preparation method of the poly (2, 3,5, 6-tetrafluoroterephthalic acid) 4, 8-tricyclo [5.2.1.O2,7] decane dimethanol ester comprises the following steps: adding 2,3,5, 6-tetrafluoroterephthalic acid, 4, 8-tricyclo [5.2.1.O2,7] decanedimethanol, dicyclohexylcarbodiimide DCC, 4-dimethylaminopyridine DMAP and a catalyst into a high boiling point solvent, stirring uniformly, transferring the mixture into a high pressure reaction kettle, replacing air in the kettle by inert gas, carrying out esterification reaction for 4.5 hours at 105 ℃, and fractionating water while reacting to obtain an oligomer; then carrying out polycondensation reaction for 4.5 hours under the condition of 50KPa and 240 ℃, after the reaction is finished, adjusting normal pressure and normal temperature, settling in water, washing the settled polymer with ethanol for 4 times, and finally drying the polymer in a vacuum drying oven at 87 ℃ to constant weight to obtain 2,3,5, 6-tetrafluoroterephthalic acid 4, 8-tricyclo [5.2.1.O2,7] decane dimethanol ester; the molar ratio of the 2,3,5, 6-tetrafluoroterephthalic acid, the 4, 8-tricyclo [5.2.1.O2,7] decanedimethanol, dicyclohexylcarbodiimide DCC, 4-dimethylaminopyridine DMAP, the catalyst and the high boiling point solvent is 1:1:0.7:0.5:0.35:7; the catalyst is a mixture formed by mixing tetrabutyl titanate and tetraisopropyl titanate according to the mass ratio of 1:0.9; the high boiling point solvent is dimethyl sulfoxide; the inert gas is helium.
The coupling agent is silane coupling agent KH560; the antioxidant is antioxidant 1076; the plasticizer is epoxidized soybean oil; the filler is calcium carbonate, and the particle size of the filler is 850 meshes; the aziridine crosslinking agent is an aziridine crosslinking agent XR-100; the molecular weight of the chitosan quaternary ammonium salt is 10 ten thousand, the substitution degree is 90%, and the chitosan quaternary ammonium salt is provided by Shanghai source leaf biotechnology Co Ltd, and the product number is S26618-500g.
A preparation process of non-woven fabric for photovoltaic table-board paper comprises the following steps: uniformly mixing PET polyester chips, carboxyl-terminated hyperbranched polyesters, poly (2, 3,5, 6-tetrafluoroterephthalic acid) 4, 8-tricyclo [5.2.1.O2,7] decane dimethanol ester, a coupling agent, an antioxidant, a plasticizer and a filler according to parts by weight to obtain a mixed material, adding the mixed material into a double-screw extruder, sequentially carrying out melt blowing, net forming, rolling into cloth by a rolling mill, soaking the modified liquid, drying and solidifying, washing by clear water, and drying to prepare non-woven fabrics for photovoltaic mesa paper; the temperature of the rolling mill during rolling is 130 ℃, and the speed of the non-woven fabric passing through the hot roller of the rolling mill is 210 revolutions per minute; the modified liquid is a mixed liquid of an aziridine crosslinking agent and chitosan quaternary ammonium salt; wherein the mass of the solvent water is 73wt% of the total mass of the mixed solution; the drying and curing temperature is 65 ℃ and the time is 2.5 hours.
Example 3
The non-woven fabric for the photovoltaic table-board paper is prepared from the following raw materials in parts by weight: 55 parts of PET polyester chip, 15 parts of carboxyl-terminated hyperbranched polyester, 20 parts of poly (2, 3,5, 6-tetrafluoroterephthalic acid) 4, 8-tricyclo [5.2.1.O2,7] decane dimethanol ester, 1.2 parts of coupling agent, 0.7 part of antioxidant, 2 parts of plasticizer, 6.5 parts of filler, 3 parts of aziridine crosslinking agent and 1 part of chitosan quaternary ammonium salt.
The PET polyester chip is a bright polyester chip BRN-24 produced by China petrochemical industry; the carboxyl-terminated hyperbranched polyester is HyPer C403 produced by Wuhan hyperbranched resin technology Co.
The preparation method of the poly (2, 3,5, 6-tetrafluoroterephthalic acid) 4, 8-tricyclo [5.2.1.O2,7] decane dimethanol ester comprises the following steps: adding 2,3,5, 6-tetrafluoroterephthalic acid, 4, 8-tricyclo [5.2.1.O2,7] decanedimethanol, dicyclohexylcarbodiimide DCC, 4-dimethylaminopyridine DMAP and a catalyst into a high boiling point solvent, stirring uniformly, transferring the mixture into a high pressure reaction kettle, replacing air in the kettle by inert gas, carrying out esterification reaction for 5 hours at 110 ℃, and fractionating water while reacting to obtain an oligomer; then carrying out polycondensation reaction for 5 hours under the condition of the reaction pressure of 60KPa and the temperature of 243 ℃, adjusting normal pressure and normal temperature after the reaction is finished, settling in water, washing the settled polymer with ethanol for 5 times, and finally drying the polymer in a vacuum drying oven at the temperature of 90 ℃ to constant weight to obtain 2,3,5, 6-tetrafluoroterephthalic acid 4, 8-tricyclo [5.2.1.O2,7] decane dimethanol ester; the molar ratio of the 2,3,5, 6-tetrafluoroterephthalic acid, the 4, 8-tricyclo [5.2.1.O2,7] decanedimethanol, dicyclohexylcarbodiimide DCC, 4-dimethylaminopyridine DMAP, the catalyst and the high boiling point solvent is 1:1:0.8:0.5:0.4:8; the catalyst is a mixture formed by mixing tetrabutyl titanate and tetraisopropyl titanate according to a mass ratio of 1:1; the high boiling point solvent is dimethyl sulfoxide; the inert gas is neon.
The coupling agent is a silane coupling agent KH570; the antioxidant is an antioxidant 1098; the plasticizer is epoxidized soybean oil; the filler is calcium carbonate, and the particle size of the filler is 900 meshes; the aziridine crosslinking agent is an aziridine crosslinking agent XR-100; the molecular weight of the chitosan quaternary ammonium salt is 10 ten thousand, the substitution degree is 90%, and the chitosan quaternary ammonium salt is provided by Shanghai source leaf biotechnology Co Ltd, and the product number is S26618-500g.
A preparation process of non-woven fabric for photovoltaic table-board paper comprises the following steps: uniformly mixing PET polyester chips, carboxyl-terminated hyperbranched polyesters, poly (2, 3,5, 6-tetrafluoroterephthalic acid) 4, 8-tricyclo [5.2.1.O2,7] decane dimethanol ester, a coupling agent, an antioxidant, a plasticizer and a filler according to parts by weight to obtain a mixed material, adding the mixed material into a double-screw extruder, sequentially carrying out melt blowing, net forming, rolling into cloth by a rolling mill, soaking the modified liquid, drying and solidifying, washing by clear water, and drying to prepare non-woven fabrics for photovoltaic mesa paper; the temperature of the rolling mill during rolling is 140 ℃, and the speed of the non-woven fabric passing through the hot roller of the rolling mill is 240 revolutions per minute; the modified liquid is a mixed liquid of an aziridine crosslinking agent and chitosan quaternary ammonium salt; wherein the mass of the solvent water is 75wt% of the total mass of the mixed solution; the drying and curing temperature is 70 ℃ and the time is 3 hours.
Example 4
The non-woven fabric for the photovoltaic table-board paper is prepared from the following raw materials in parts by weight: 58 parts of PET polyester chip, 18 parts of carboxyl-terminated hyperbranched polyester, 23 parts of poly (2, 3,5, 6-tetrafluoroterephthalic acid) 4, 8-tricyclo [5.2.1.O2,7] decane dimethanol ester, 1.3 parts of coupling agent, 0.9 part of antioxidant, 2.5 parts of plasticizer, 7.5 parts of filler, 3.5 parts of aziridine crosslinking agent and 1.3 parts of chitosan quaternary ammonium salt.
The PET polyester chip is a bright polyester chip BRN-24 produced by China petrochemical industry; the carboxyl-terminated hyperbranched polyester is a mixture formed by mixing HyPer C403 and HyPer C404 produced by Wuhan hyperbranched resin technology Co., ltd.
The preparation method of the poly (2, 3,5, 6-tetrafluoroterephthalic acid) 4, 8-tricyclo [5.2.1.O2,7] decane dimethanol ester comprises the following steps: adding 2,3,5, 6-tetrafluoroterephthalic acid, 4, 8-tricyclo [5.2.1.O2,7] decanedimethanol, dicyclohexylcarbodiimide DCC, 4-dimethylaminopyridine DMAP and a catalyst into a high boiling point solvent, stirring uniformly, transferring the mixture into a high pressure reaction kettle, replacing air in the kettle by inert gas, carrying out esterification reaction at 118 ℃ for 5.5 hours, and fractionating water while reacting to obtain an oligomer; then carrying out polycondensation reaction for 5.5 hours at the reaction pressure of 70KPa and 248 ℃, after the reaction is finished, adjusting normal pressure and normal temperature, settling in water, washing the settled polymer with ethanol for 6 times, and finally drying the polymer in a vacuum drying oven at 93 ℃ to constant weight to obtain 2,3,5, 6-tetrafluoroterephthalic acid 4, 8-tricyclo [5.2.1.O2,7] decane dimethanol ester; the molar ratio of the 2,3,5, 6-tetrafluoroterephthalic acid, the 4, 8-tricyclo [5.2.1.O2,7] decanedimethanol, dicyclohexylcarbodiimide DCC, 4-dimethylaminopyridine DMAP, the catalyst and the high boiling point solvent is 1:1:0.9:0.5:0.45:9; the catalyst is a mixture formed by mixing tetrabutyl titanate and tetraisopropyl titanate according to a mass ratio of 1:1.1; the high boiling point solvent is dimethyl sulfoxide; the inert gas is nitrogen.
The coupling agent is a mixture formed by mixing a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH570 according to a mass ratio of 1:2:2; the antioxidant is a mixture formed by mixing an antioxidant 1010, an antioxidant 1076, an antioxidant 1098 and an antioxidant 168 according to a mass ratio of 1:1:2:2; the plasticizer is epoxidized soybean oil; the filler is calcium carbonate, and the particle size of the filler is 950 meshes; the aziridine crosslinking agent is an aziridine crosslinking agent XR-100; the molecular weight of the chitosan quaternary ammonium salt is 10 ten thousand, the substitution degree is 90%, and the chitosan quaternary ammonium salt is provided by Shanghai source leaf biotechnology Co Ltd, and the product number is S26618-500g.
A preparation process of non-woven fabric for photovoltaic table-board paper comprises the following steps: uniformly mixing PET polyester chips, carboxyl-terminated hyperbranched polyesters, poly (2, 3,5, 6-tetrafluoroterephthalic acid) 4, 8-tricyclo [5.2.1.O2,7] decane dimethanol ester, a coupling agent, an antioxidant, a plasticizer and a filler according to parts by weight to obtain a mixed material, adding the mixed material into a double-screw extruder, sequentially carrying out melt blowing, net forming, rolling into cloth by a rolling mill, soaking the modified liquid, drying and solidifying, washing by clear water, and drying to prepare non-woven fabrics for photovoltaic mesa paper; the temperature of the rolling mill during rolling is 155 ℃, and the speed of the non-woven fabric passing through the hot roller of the rolling mill is 290 rpm; the modified liquid is a mixed liquid of an aziridine crosslinking agent and chitosan quaternary ammonium salt; wherein the mass of the solvent water is 78wt% of the total mass of the mixed solution; the drying and curing temperature is 75 ℃ and the time is 3.5 hours.
Example 5
The non-woven fabric for the photovoltaic table-board paper is prepared from the following raw materials in parts by weight: 60 parts of PET polyester chip, 20 parts of carboxyl-terminated hyperbranched polyester, 25 parts of poly (2, 3,5, 6-tetrafluoroterephthalic acid) 4, 8-tricyclo [5.2.1.O2,7] decane dimethanol ester, 1.5 parts of coupling agent, 1 part of antioxidant, 3 parts of plasticizer, 8 parts of filler, 4 parts of aziridine crosslinking agent and 1.5 parts of chitosan quaternary ammonium salt.
The PET polyester chip is a bright polyester chip BRN-24 produced by China petrochemical industry; the carboxyl-terminated hyperbranched polyester is HyPer C403 produced by Wuhan hyperbranched resin technology Co.
The preparation method of the poly (2, 3,5, 6-tetrafluoroterephthalic acid) 4, 8-tricyclo [5.2.1.O2,7] decane dimethanol ester comprises the following steps: adding 2,3,5, 6-tetrafluoroterephthalic acid, 4, 8-tricyclo [5.2.1.O2,7] decanedimethanol, dicyclohexylcarbodiimide DCC, 4-dimethylaminopyridine DMAP and a catalyst into a high boiling point solvent, stirring uniformly, transferring the mixture into a high pressure reaction kettle, replacing air in the kettle by inert gas, carrying out esterification reaction for 6 hours at 120 ℃, and fractionating water while reacting to obtain an oligomer; then carrying out polycondensation reaction for 6 hours under the conditions of 80KPa and 250 ℃, after the reaction is finished, adjusting normal pressure and normal temperature, settling in water, washing the settled polymer with ethanol for 6 times, and finally drying the polymer in a vacuum drying oven at 95 ℃ to constant weight to obtain 2,3,5, 6-tetrafluoroterephthalic acid 4, 8-tricyclo [5.2.1.O2,7] decane dimethanol ester; the molar ratio of the 2,3,5, 6-tetrafluoroterephthalic acid, the 4, 8-tricyclo [5.2.1.O2,7] decanedimethanol, dicyclohexylcarbodiimide DCC, 4-dimethylaminopyridine DMAP, the catalyst and the high boiling point solvent is 1:1:1:0.5:0.5:10; the catalyst is a mixture formed by mixing tetrabutyl titanate and tetraisopropyl titanate according to a mass ratio of 1:1.2.
The high boiling point solvent is dimethyl sulfoxide; the inert gas is nitrogen; the coupling agent is a silane coupling agent KH550; the antioxidant is antioxidant 168; the plasticizer is epoxidized soybean oil; the filler is calcium carbonate, and the particle size of the filler is 1000 meshes; the aziridine crosslinking agent is an aziridine crosslinking agent XR-100; the molecular weight of the chitosan quaternary ammonium salt is 10 ten thousand, the substitution degree is 90%, and the chitosan quaternary ammonium salt is provided by Shanghai source leaf biotechnology Co Ltd, and the product number is S26618-500g.
A preparation process of non-woven fabric for photovoltaic table-board paper comprises the following steps: uniformly mixing PET polyester chips, carboxyl-terminated hyperbranched polyesters, poly (2, 3,5, 6-tetrafluoroterephthalic acid) 4, 8-tricyclo [5.2.1.O2,7] decane dimethanol ester, a coupling agent, an antioxidant, a plasticizer and a filler according to parts by weight to obtain a mixed material, adding the mixed material into a double-screw extruder, sequentially carrying out melt blowing, net forming, rolling into cloth by a rolling mill, soaking the modified liquid, drying and solidifying, washing by clear water, and drying to prepare non-woven fabrics for photovoltaic mesa paper; the temperature of the rolling mill during rolling is 160 ℃, and the speed of the non-woven fabric passing through the hot roller of the rolling mill is 300 revolutions per minute; the modified liquid is a mixed liquid of an aziridine crosslinking agent and chitosan quaternary ammonium salt; wherein the mass of the solvent water is 80wt% of the total mass of the mixed solution; the drying and curing temperature is 80 ℃ and the time is 4 hours.
Comparative example 1
A non-woven fabric for photovoltaic mesa paper has a formula and a preparation process similar to those of example 1, except that PET polyester chips are used for replacing poly (2, 3,5, 6-tetrafluoroterephthalic acid) 4, 8-tricyclo [5.2.1.O2,7] decane dimethanol ester, and an aziridine crosslinking agent is not added.
Comparative example 2
The formula and preparation process of the non-woven fabric for the photovoltaic mesa paper are similar to those of the example 1, except that the PET polyester chips are used for replacing carboxyl-terminated hyperbranched polyester, and chitosan quaternary ammonium salt is not added.
In order to further illustrate the beneficial technical effects of the nonwoven fabrics for photovoltaic mesa paper made in the examples of the present invention, the nonwoven fabrics for photovoltaic mesa paper made in examples 1 to 5 and comparative examples 1 to 2 were subjected to the relevant performance test, the test results are shown in table 1, and the test methods are as follows:
(1) Breaking strength of nonwoven fabric: the test was carried out according to standard GB/T24218.5-2016.
(2) Ageing resistance: after the nonwoven fabric was placed in hot air at 85 ℃ for 96 hours, the retention rate of burst strength was tested and calculated, and the larger the value, the better the aging resistance.
(3) Smoothness: the test was performed using an EBO1 of Asahi-seiko digital type Wang Yan smoothness tester of Japanese.
(4) Air permeability: the test was carried out with reference to the method in standard GB/T24218.15-2018.
TABLE 1
| Project | Bursting strength | Front smoothness | Aging resistance | Air permeability |
| Unit (B) | N | S | % | cfm |
| Example 1 | 1230 | 29 | 98.8 | 6.6 |
| Example 2 | 1236 | 32 | 99.1 | 6.7 |
| Example 3 | 1240 | 33 | 99.6 | 7.0 |
| Example 4 | 1248 | 35 | 99.8 | 7.2 |
| Example 5 | 1253 | 36 | 99.9 | 7.5 |
| Comparative example 1 | 928 | 27 | 92.6 | 6.4 |
| Comparative example 2 | 916 | 25 | 94.2 | 6.0 |
As can be seen from table 1, the nonwoven fabric for photovoltaic mesa paper disclosed in the examples of the present invention has more excellent mechanical properties, aging resistance, smoothness and air permeability. The addition of poly (2, 3,5, 6-tetrafluoroterephthalic acid) 4, 8-tricyclo [5.2.1.O2,7] decanedimethanol ester (CAS: 26896-48-0), aziridine crosslinking agent, carboxyl terminated hyperbranched polyester, chitosan quaternary ammonium salt is beneficial for improving the above properties.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention, which is defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.