CN111560772A - High-strength hydrophobic non-woven fabric and preparation method thereof - Google Patents

High-strength hydrophobic non-woven fabric and preparation method thereof Download PDF

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CN111560772A
CN111560772A CN202010510453.4A CN202010510453A CN111560772A CN 111560772 A CN111560772 A CN 111560772A CN 202010510453 A CN202010510453 A CN 202010510453A CN 111560772 A CN111560772 A CN 111560772A
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fiber web
spunlace
reaction
methyl acrylate
dipentaerythritol
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CN111560772B (en
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廖国庆
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Meiwa Plastic Shanghai Co Ltd
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Changsha Rouzhi New Material Technology Co ltd
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M14/00Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/18Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
    • D06M14/20Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of natural origin
    • D06M14/22Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of natural origin of vegetal origin, e.g. cellulose or derivatives thereof
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/425Cellulose series
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/44Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling
    • D04H1/46Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres
    • D04H1/492Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres by fluid jet
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02Natural fibres, other than mineral fibres
    • D06M2101/04Vegetal fibres
    • D06M2101/06Vegetal fibres cellulosic
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10Repellency against liquids
    • D06M2200/12Hydrophobic properties
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/62Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention relates to the technical field of non-woven fabrics, and discloses a high-strength hydrophobic non-woven fabric and a preparation method thereof, wherein the non-woven fabric comprises the following raw materials in parts by weight: 100 parts of cellulose fiber, 5-10 parts of trihydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer, 30-35 parts of 1, 6-bis (acryloyloxy) -2,2,3,3,4,4,5, 5-octafluorohexane and 2-2.5 parts of pentaerythritol tetraacrylate. According to the invention, the strength of the non-woven fabric is improved by adding the trihydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer into the non-woven fabric; the strength and the hydrophobicity of the non-woven fabric are improved by grafting 1, 6-di (acryloyloxy) -2,2,3,3,4,4,5, 5-octafluorohexane and pentaerythritol tetraacrylate on the surface of the non-woven fabric.

Description

High-strength hydrophobic non-woven fabric and preparation method thereof
Technical Field
The invention relates to the technical field of non-woven fabrics, in particular to a high-strength hydrophobic non-woven fabric and a preparation method thereof.
Background
Nonwoven fabrics, also known as nonwovens, are sheets, webs, or batts made of oriented or randomly arranged fibers that are bonded to one another by abrasion, cohesion, or bonding, or a combination of these methods. Due to the characteristics of wide raw materials, short production flow, low cost and the like, the non-woven fabric is widely applied to the fields of civil textiles and industrial textiles. Among various raw materials for producing nonwoven fabrics, cellulose-based nonwoven fabrics have unique applications in medical, nursing, hygienic, cosmetic and other industrial fields because cellulose fibers have properties that cannot be possessed by a series of synthetic fibers, such as easy manageability and easy biodegradability. However, cellulose-based nonwoven fabrics cannot be used in applications requiring water repellency due to their high water absorption.
At present, the hydrophobic modification method for cellulose fiber fabric mostly focuses on water and oil repellent finishing of the fabric by using nano materials, namely, a proper super-hydrophobic nano particle special function mother solution is adopted to carry out padding treatment and sizing treatment on the fiber surface, the nano particles are highly dispersed among yarns, among fibers and on the fiber surface through the combination of the adhesive and the fibers, the nano particles and the adhesive are in concave-convex arrangement on the fiber surface, and a nano-sized air film is formed in a nano-sized groove, so that the hydrophobicity of the fabric surface is improved. However, the hydrophobic fabric obtained by this method has poor durability, and the nanoparticles are not firmly bonded to the fabric, and easily fall off to affect the hydrophobicity of the fabric.
Disclosure of Invention
In order to solve the technical problems, the invention provides a high-strength hydrophobic non-woven fabric and a preparation method thereof. The non-woven fabric has good hydrophobicity, and the hydrophobic interface is firmly combined with the non-woven fabric, so that the non-woven fabric has good durability; in addition, the non-woven fabric has high strength, is durable and is not easy to damage.
The specific technical scheme of the invention is as follows:
a high-strength hydrophobic non-woven fabric comprises the following raw materials in parts by weight: 100 parts of cellulose fiber, 5-10 parts of trihydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer, 30-35 parts of 1, 6-bis (acryloyloxy) -2,2,3,3,4,4,5, 5-octafluorohexane and 2-2.5 parts of pentaerythritol tetraacrylate.
A method for preparing the high-strength hydrophobic non-woven fabric comprises the following steps:
(1) loosening cellulose fibers, and dispersing the loosened cellulose fibers in water to prepare a fiber suspension;
(2) mixing the fiber suspension with a trihydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer, and performing wet-laid to prepare a fiber web;
(3) carrying out spunlace reinforcement, washing and drying on the fiber web to obtain a spunlace fiber web;
(4) 1, 6-bis (acryloyloxy) -2,2,3,3,4,4,5, 5-octafluorohexane and pentaerythritol tetraacrylate are taken as grafting monomers, and ultraviolet surface grafting is carried out on the spunlace fiber web to obtain a fiber web subjected to grafting treatment;
(5) and cutting the grafted fiber web to obtain the high-strength hydrophobic non-woven fabric.
In the invention, the trihydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer and the cellulose fiber are blended and exist in the non-woven fabric, and the strength of the non-woven fabric is enhanced, and the mechanism is as follows: the trihydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer has a large number of terminal hydroxyl groups, and can form hydrogen bonds with free hydroxyl groups in cellulose fibers, so that more hydrogen bonds exist in a crosslinking area of the cellulose fibers, the crosslinking degree of the fibers is improved, and the strength of the non-woven fabric is increased; meanwhile, the terpolymer molecules have higher branching degree and can be crosslinked with cellulose fibers in all directions, so that the crosslinking degree of the fibers can be further improved, and the strength of the non-woven fabric is increased.
Since there are few hydroxyl groups liberated from cellulose fibers in the process of manufacturing a nonwoven fabric, the strength of the nonwoven fabric is improved to a limited extent by the tris/hydroxymethyl aminomethane/methylacrylate/dipentaerythritol copolymer. According to the invention, 1, 6-di (acryloyloxy) -2,2,3,3,4,4,5, 5-octafluorohexane and pentaerythritol tetraacrylate are grafted on the surface of the non-woven fabric, so that the strength of the non-woven fabric is further increased, and meanwhile, the non-woven fabric can obtain hydrophobicity, and the mechanism is as follows: the two grafting monomers are grafted to the surface of the spunlace fiber web through carbon-carbon double bonds; meanwhile, a plurality of carbon-carbon double bonds exist in the two grafting monomers, and the carbon-carbon double bonds can generate photoinitiated polymerization reaction, so that a cross-linked network-shaped structure is formed on the surface of the spunlace fiber web, and the strength of the non-woven fabric is increased; meanwhile, the fluorine-containing group in the 1, 6-bis (acryloyloxy) -2,2,3,3,4,4,5, 5-octafluorohexane has better hydrophobicity, can form a hydrophobic interface on the surface of the non-woven fabric, and is not easy to fall off and has better durability because the hydrophobic interface is grafted on the surface of the non-woven fabric through a covalent bond.
Preferably, the tris-hydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer is a terpolymer modified by carboxyl grafting, and the modification method is as follows:
(a) ring opening reaction: dissolving a trihydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer in N, N-dimethylformamide, adding a ring-opening reaction catalyst, dropwise adding an N, N-dimethylformamide solution of 2-oxaproyl ethyl acetate, and reacting for 2-3 h at the temperature of 70-80 ℃; after the reaction is finished, carrying out reduced pressure distillation to remove the N, N-dimethylformamide and obtain a ring-opening reaction product;
(b) and (3) hydrolysis reaction: dissolving the ring-opening reaction product obtained in the step (a) in water, adding a sodium hydroxide solution, and reacting at 60-70 ℃ for 1-2 h; after the reaction is finished, the water is removed by reduced pressure distillation, and the terpolymer modified by carboxyl grafting is obtained.
A method for preparing the high-strength hydrophobic non-woven fabric comprises the following steps:
(1) loosening cellulose fibers, and dispersing the loosened cellulose fibers in water to prepare a fiber suspension;
(2) adding an esterification reaction catalyst into the fiber suspension, dropwise adding an aqueous solution of a carboxyl graft modified terpolymer under stirring, and reacting for 2-3 h at 80-85 ℃; after the reaction is finished, wet-laying to prepare a fiber web;
(3) carrying out spunlace reinforcement, washing and drying on the fiber web to obtain a spunlace fiber web;
(4) 1, 6-bis (acryloyloxy) -2,2,3,3,4,4,5, 5-octafluorohexane and pentaerythritol tetraacrylate are taken as grafting monomers, and ultraviolet surface grafting is carried out on the spunlace fiber web to obtain a fiber web subjected to grafting treatment;
(5) and cutting the grafted fiber web to obtain the high-strength hydrophobic non-woven fabric.
The trihydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer is grafted with carboxyl by modification, the carboxyl is subjected to esterification reaction with hydroxyl in cellulose fiber in the step (2), covalent crosslinking is formed between the terpolymer and the cellulose fiber, and compared with hydrogen bonds, the covalent crosslinking has larger bond energy, so that the strength of the non-woven fabric can be further improved.
Preferably, the method for preparing the tris-hydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer is as follows:
(i) addition reaction: adding trihydroxymethyl aminomethane into a methanol water solution, heating to 30-35 ℃, and stirring for dissolving; dropwise adding a methanol solution of methyl acrylate, and reacting for 2-3 h at the temperature of 30-35 ℃; after the reaction is finished, vacuumizing to remove methanol, water and excessive methyl acrylate to obtain an addition reaction product;
(ii) ester exchange reaction: adding dipentaerythritol into dimethyl sulfoxide, heating to 90-100 ℃, and stirring for dissolving; dropwise adding the addition reaction product obtained in the step (i), heating to 125-130 ℃, reacting for 2-3 h, and reacting for 1.5-2.5 h at 100-110 ℃ and 0.05-0.08 MPa; and after the reaction is finished, performing reduced pressure rotary evaporation to remove dimethyl sulfoxide to obtain the trihydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer.
In the step (i), amino in the trihydroxymethyl aminomethane and carbon-carbon double bond in the methyl acrylate are subjected to addition reaction; in the step (ii), the hydroxyl groups in the addition reaction product and the dipentaerythritol undergo transesterification with the ester groups in the addition reaction product, thereby obtaining the copolymer. The terpolymer prepared by the method contains a large number of terminal hydroxyl groups, has higher branching degree, and can effectively improve the strength of the non-woven fabric.
Preferably, in the step (i), the mass ratio of the tris (hydroxymethyl) aminomethane to the methyl acrylate is 1:1 to 1.5.
Preferably, the mass ratio of dipentaerythritol in step (ii) to tris (hydroxymethyl) aminomethane in step (i) is 1:3.5 to 4.
Preferably, in the step (a), the mass ratio of the tris-hydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer to the 2-oxaproyl ethyl acetate is 1: 1.5-2.
Preferably, in the step (a), the ring-opening reaction catalyst is at least one of a tertiary amine and a quaternary ammonium salt.
Preferably, in the step (4), the method of ultraviolet surface grafting is as follows: dissolving 1, 6-bis (acryloyloxy) -2,2,3,3,4,4,5, 5-octafluorohexane, pentaerythritol tetraacrylate and a photoinitiator in acetone to prepare a mixed solution; immersing the spunlace fiber web into the mixed solution, and carrying out grafting reaction under ultraviolet light; after the reaction, the spunlace fiber web is transferred into acetone, monomers and polymers which are not grafted to the spunlace fiber web are removed through ultrasonic treatment, and the monomers and polymers which are not grafted to the spunlace fiber web are further removed through acetone extraction.
Under the irradiation of ultraviolet light, hydrogen on the surface of the cellulose is abstracted by a photoinitiator, so that free radicals are generated on the surface of the cellulose, and are combined with carbon-carbon double bonds in the grafting monomer 1, 6-bis (acryloyloxy) -2,2,3,3,4,4,5, 5-octafluorohexane and pentaerythritol tetraacrylate, thereby initiating the grafting reaction and the polymerization reaction of the grafting monomer on the surface of the cellulose.
Preferably, the mass fraction of the 1, 6-bis (acryloyloxy) -2,2,3,3,4,4,5, 5-octafluorohexane in acetone is 40% to 50%.
Preferably, the photoinitiator is benzophenone; the mass fraction of the photoinitiator in acetone is 4.5-5%.
Compared with the prior art, the invention has the following advantages:
(1) the strength of the non-woven fabric can be improved by adding the trihydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer into the non-woven fabric;
(2) the strength of the non-woven fabric can be further improved by grafting a cross-linked network formed by 1, 6-di (acryloyloxy) -2,2,3,3,4,4,5, 5-octafluorohexane and pentaerythritol tetraacrylate on the surface of the non-woven fabric, and the non-woven fabric is endowed with a hydrophobic surface which has better durability.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
A nonwoven fabric was prepared by the following method:
(1) the preparation method of the trihydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer comprises the following specific steps:
(1.1) addition reaction: adding 5.2g of tris (hydroxymethyl) aminomethane into 10mL of 50% methanol aqueous solution (50% methanol aqueous solution, namely 50% by volume of methanol), heating to 30 ℃, and stirring for dissolving; dropwise adding a mixed solution of 5.2g of methyl acrylate and 10mL of methanol, and reacting for 2h at 30 ℃; after the reaction is finished, vacuumizing to remove methanol, water and excessive methyl acrylate to obtain an addition reaction product;
(1.2) transesterification: adding 1.3g of dipentaerythritol into 10mL of dimethyl sulfoxide, heating to 90 ℃, and stirring for dissolving; dropwise adding the addition reaction product obtained in the step (1.1), heating to 125 ℃, reacting for 2h, and reacting for 2h at 100 ℃ and 0.08 MPa; after the reaction is finished, performing reduced pressure rotary evaporation to remove dimethyl sulfoxide to obtain a trihydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer;
(2) loosening 100g of cellulose fibers, and dispersing into water to prepare a fiber suspension;
(3) mixing the fiber suspension with 5g of the trihydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer obtained in the step (1), and performing wet-laid to prepare a fiber web;
(4) carrying out spunlace reinforcement, washing and drying on the fiber web to obtain a spunlace fiber web;
(5) 1, 6-di (acryloyloxy) -2,2,3,3,4,4,5, 5-octafluorohexane and pentaerythritol tetraacrylate are taken as grafting monomers, ultraviolet surface grafting is carried out on the spunlace fiber web, and the fiber web after grafting treatment is obtained, and the specific process is as follows:
(5.1) preparing a mixed solution by dissolving 30g of 1, 6-bis (acryloyloxy) -2,2,3,3,4,4,5, 5-octafluorohexane, 2g of pentaerythritol tetraacrylate and 1.5g of benzophenone in 45g of acetone;
(5.2) immersing the spunlace fiber web into the mixed solution prepared in the step (5.1), and reacting for 1min under 365nm ultraviolet light;
(5.3) after the reaction is finished, transferring the spunlace fiber web into acetone, and carrying out ultrasonic treatment for 20min at 40W to remove monomers and polymers which are not grafted on the spunlace fiber web; extracting with acetone for 5h, and further removing the monomers and polymers which are not grafted on the spunlace fiber web;
(6) and cutting the fiber web subjected to the grafting treatment to obtain the non-woven fabric.
Example 2
A nonwoven fabric was prepared by the following method:
(1) the preparation method of the trihydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer comprises the following specific steps:
(1.1) addition reaction: adding 6.5g of tris (hydroxymethyl) aminomethane into 10mL of 50% methanol aqueous solution (50% methanol aqueous solution, namely 50% by volume of methanol), heating to 33 ℃, and stirring for dissolving; dropwise adding a mixed solution of 7.8g of methyl acrylate and 12mL of methanol, and reacting for 2.5h at 33 ℃; after the reaction is finished, vacuumizing to remove methanol, water and excessive methyl acrylate to obtain an addition reaction product;
(1.2) transesterification: adding 1.7g of dipentaerythritol into 10mL of dimethyl sulfoxide, heating to 95 ℃, and stirring for dissolving; dropwise adding the addition reaction product obtained in the step (1.1), heating to 127 ℃, reacting for 2.5h, and reacting for 2h at 105 ℃ under 0.06 MPa; after the reaction is finished, performing reduced pressure rotary evaporation to remove dimethyl sulfoxide to obtain a trihydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer;
(2) loosening 100g of cellulose fibers, and dispersing into water to prepare a fiber suspension;
(3) mixing the fiber suspension with 8g of the trihydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer obtained in the step (1), and performing wet-laid to prepare a fiber web;
(4) carrying out spunlace reinforcement, washing and drying on the fiber web to obtain a spunlace fiber web;
(5) 1, 6-di (acryloyloxy) -2,2,3,3,4,4,5, 5-octafluorohexane and pentaerythritol tetraacrylate are taken as grafting monomers, ultraviolet surface grafting is carried out on the spunlace fiber web, and the fiber web after grafting treatment is obtained, and the specific process is as follows:
(5.1) A mixed solution was prepared by dissolving 32g of 1, 6-bis (acryloyloxy) -2,2,3,3,4,4,5, 5-octafluorohexane, 2.3g of pentaerythritol tetraacrylate and 1.6g of benzophenone in 33g of acetone;
(5.2) immersing the spunlace fiber web into the mixed solution prepared in the step (5.1), and reacting for 1.5min under 365nm ultraviolet light;
(5.3) after the reaction is finished, transferring the spunlace fiber web into acetone, and carrying out ultrasonic treatment for 20min at 40W to remove monomers and polymers which are not grafted on the spunlace fiber web; extracting with acetone for 5h, and further removing the monomers and polymers which are not grafted on the spunlace fiber web;
(6) and cutting the fiber web subjected to the grafting treatment to obtain the non-woven fabric.
Example 3
A nonwoven fabric was prepared by the following method:
(1) the preparation method of the trihydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer comprises the following specific steps:
(1.1) addition reaction: adding 7.2g of tris (hydroxymethyl) aminomethane into 15mL of 50% methanol aqueous solution (50% methanol aqueous solution, namely 50% by volume of methanol), heating to 35 ℃, and stirring for dissolving; dropwise adding a mixed solution of 10.8g of methyl acrylate and 15mL of methanol, and reacting for 3h at 35 ℃; after the reaction is finished, vacuumizing to remove methanol, water and excessive methyl acrylate to obtain an addition reaction product;
(1.2) transesterification: adding 2g of dipentaerythritol into 10mL of dimethyl sulfoxide, heating to 100 ℃, and stirring for dissolving; dropwise adding the addition reaction product obtained in the step (1.1), heating to 130 ℃, reacting for 3h, and reacting for 2.5h at 110 ℃ under 0.05 MPa; after the reaction is finished, performing reduced pressure rotary evaporation to remove dimethyl sulfoxide to obtain a trihydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer;
(2) loosening 100g of cellulose fibers, and dispersing into water to prepare a fiber suspension;
(3) mixing the fiber suspension with 10g of the trihydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer obtained in the step (1), and performing wet-laid to prepare a fiber web;
(4) carrying out spunlace reinforcement, washing and drying on the fiber web to obtain a spunlace fiber web;
(5) 1, 6-di (acryloyloxy) -2,2,3,3,4,4,5, 5-octafluorohexane and pentaerythritol tetraacrylate are taken as grafting monomers, ultraviolet surface grafting is carried out on the spunlace fiber web, and the fiber web after grafting treatment is obtained, and the specific process is as follows:
(5.1) 35g of 1, 6-bis (acryloyloxy) -2,2,3,3,4,4,5, 5-octafluorohexane, 2.5g of pentaerythritol tetraacrylate and 1.7g of benzophenone were dissolved in 35g of acetone to prepare a mixed solution;
(5.2) immersing the spunlace fiber web into the mixed solution prepared in the step (5.1), and reacting for 1.5min under 365nm ultraviolet light;
(5.3) after the reaction is finished, transferring the spunlace fiber web into acetone, and carrying out ultrasonic treatment for 20min at 40W to remove monomers and polymers which are not grafted on the spunlace fiber web; extracting with acetone for 5h, and further removing the monomers and polymers which are not grafted on the spunlace fiber web;
(6) and cutting the fiber web subjected to the grafting treatment to obtain the non-woven fabric.
Example 4
A nonwoven fabric was prepared by the following method:
(1) the preparation method of the trihydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer comprises the following specific steps:
(1.1) addition reaction: adding 5.2g of tris (hydroxymethyl) aminomethane into 10mL of 50% methanol aqueous solution (50% methanol aqueous solution, namely 50% by volume of methanol), heating to 30 ℃, and stirring for dissolving; dropwise adding a mixed solution of 5.2g of methyl acrylate and 10mL of methanol, and reacting for 2h at 30 ℃; after the reaction is finished, vacuumizing to remove methanol, water and excessive methyl acrylate to obtain an addition reaction product;
(1.2) transesterification: adding 1.3g of dipentaerythritol into 10mL of dimethyl sulfoxide, heating to 90 ℃, and stirring for dissolving; dropwise adding the addition reaction product obtained in the step (1.1), heating to 125 ℃, reacting for 2h, and reacting for 2h at 100 ℃ and 0.08 MPa; after the reaction is finished, performing reduced pressure rotary evaporation to remove dimethyl sulfoxide to obtain a trihydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer;
(2) the preparation method of the carboxyl graft modified terpolymer comprises the following specific steps:
(2.1) Ring opening reaction: dissolving 5g of trihydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer in 10mLN, N-dimethylformamide, adding 0.1g of ring-opening reaction catalyst tetrabutylammonium bromide, dropwise adding a mixed solution of 8g of ethyl 2-oxaproyl cycloacetate and 15mLN, N-dimethylformamide, and reacting for 3 hours at 75 ℃; after the reaction is finished, carrying out reduced pressure distillation to remove the N, N-dimethylformamide and obtain a ring-opening reaction product;
(2.2) hydrolysis reaction: dissolving the ring-opening reaction product obtained in the step (2.1) in 20mL of water, adding a sodium hydroxide solution, and reacting for 1h at 65 ℃; after the reaction is finished, the water is removed by reduced pressure distillation, and the terpolymer modified by carboxyl grafting is obtained.
(3) Loosening 100g of cellulose fibers, and dispersing into water to prepare a fiber suspension;
(4) 0.15g of ZnCl as esterification catalyst was added to the fibre suspension2Dropwise adding the aqueous solution of the carboxyl graft modified terpolymer obtained in the step (2) under stirring, and reacting for 2h at 85 ℃; after the reaction is finished, wet-laying to prepare a fiber web;
(5) carrying out spunlace reinforcement, washing and drying on the fiber web to obtain a spunlace fiber web;
(6) 1, 6-di (acryloyloxy) -2,2,3,3,4,4,5, 5-octafluorohexane and pentaerythritol tetraacrylate are taken as grafting monomers, ultraviolet surface grafting is carried out on the spunlace fiber web, and the fiber web after grafting treatment is obtained, and the specific process is as follows:
(6.1) preparing a mixed solution by dissolving 30g of 1, 6-bis (acryloyloxy) -2,2,3,3,4,4,5, 5-octafluorohexane, 2g of pentaerythritol tetraacrylate and 1.5g of benzophenone in 45g of acetone;
(6.2) immersing the spunlace fiber web into the mixed solution prepared in the step (6.1), and reacting for 1min under 365nm ultraviolet light;
(6.3) after the reaction is finished, transferring the spunlace fiber web into acetone, and carrying out ultrasonic treatment for 20min at 40W to remove monomers and polymers which are not grafted on the spunlace fiber web; extracting with acetone for 5h, and further removing the monomers and polymers which are not grafted on the spunlace fiber web;
(7) and cutting the fiber web subjected to the grafting treatment to obtain the non-woven fabric.
Comparative example 1
A nonwoven fabric was prepared by the following method:
(1) loosening 100g of cellulose fibers, and dispersing into water to prepare a fiber suspension;
(2) wet-laying the fiber suspension to prepare a fiber web;
(3) carrying out spunlace reinforcement, washing and drying on the fiber web to obtain a spunlace fiber web;
(4) and cutting the spunlace fiber web to obtain the non-woven fabric.
Comparative example 2
A nonwoven fabric was prepared by the following method:
(1) the preparation method of the trihydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer comprises the following specific steps:
(1.1) addition reaction: adding 5.2g of tris (hydroxymethyl) aminomethane into 10mL of 50% methanol aqueous solution (50% methanol aqueous solution, namely 50% by volume of methanol), heating to 30 ℃, and stirring for dissolving; dropwise adding a mixed solution of 5.2g of methyl acrylate and 10mL of methanol, and reacting for 2h at 30 ℃; after the reaction is finished, vacuumizing to remove methanol, water and excessive methyl acrylate to obtain an addition reaction product;
(1.2) transesterification: adding 1.3g of dipentaerythritol into 10mL of dimethyl sulfoxide, heating to 90 ℃, and stirring for dissolving; dropwise adding the addition reaction product obtained in the step (1.1), heating to 125 ℃, reacting for 2h, and reacting for 2h at 100 ℃ and 0.08 MPa; after the reaction is finished, performing reduced pressure rotary evaporation to remove dimethyl sulfoxide to obtain a trihydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer;
(2) loosening 100g of cellulose fibers, and dispersing into water to prepare a fiber suspension;
(3) mixing the fiber suspension with 5g of the trihydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer obtained in the step (1), and performing wet-laid to prepare a fiber web;
(4) carrying out spunlace reinforcement, washing and drying on the fiber web to obtain a spunlace fiber web;
(5) and cutting the spunlace fiber web to obtain the non-woven fabric.
Comparative example 3
A nonwoven fabric was prepared by the following method:
(1) loosening 100g of cellulose fibers, and dispersing into water to prepare a fiber suspension;
(2) wet-laying the fiber suspension to prepare a fiber web;
(3) carrying out spunlace reinforcement, washing and drying on the fiber web to obtain a spunlace fiber web;
(4) 1, 6-di (acryloyloxy) -2,2,3,3,4,4,5, 5-octafluorohexane and pentaerythritol tetraacrylate are taken as grafting monomers, ultraviolet surface grafting is carried out on the spunlace fiber web, and the fiber web after grafting treatment is obtained, and the specific process is as follows:
(4.1) preparing a mixed solution by dissolving 30g of 1, 6-bis (acryloyloxy) -2,2,3,3,4,4,5, 5-octafluorohexane, 2g of pentaerythritol tetraacrylate and 1.5g of benzophenone in 45g of acetone;
(4.2) immersing the spunlace fiber web into the mixed solution prepared in the step (5.1), and reacting for 1min under 365nm ultraviolet light;
(4.3) after the reaction is finished, transferring the spunlace fiber web into acetone, and carrying out ultrasonic treatment for 20min at 40W to remove monomers and polymers which are not grafted on the spunlace fiber web; extracting with acetone for 5h, and further removing the monomers and polymers which are not grafted on the spunlace fiber web;
(5) and cutting the fiber web subjected to the grafting treatment to obtain the non-woven fabric.
The nonwoven fabrics obtained in examples 1 to 4 and comparative examples 1 to 3 were subjected to thickness, grammage, tensile strength and hydrostatic pressure tests, and the results are shown in table 1. Wherein the tensile strength is used to characterize the strength of the nonwoven; hydrostatic pressure is used to characterize the hydrophobicity of the nonwoven, with greater hydrostatic pressure indicating greater hydrophobicity of the nonwoven.
TABLE 1
Figure BDA0002528190310000091
Example 1 is different from comparative example 1 in that in example 1, tris (hydroxymethyl) aminomethane-methyl acrylate-dipentaerythritol copolymer is added to the interior of the nonwoven fabric through steps (1) and (3), and 1, 6-bis (acryloyloxy) -2,2,3,3,4,4,5, 5-octafluorohexane and pentaerythritol tetraacrylate are grafted to the surface of the nonwoven fabric through step (5), while comparative example 1 is a prior art in which the above copolymer is not added and surface grafting is not performed. Comparing the test results of the two in table 1, it was found that the tensile strength and hydrostatic pressure of the nonwoven fabric prepared in example 1 were significantly greater than those of comparative example 1, indicating that the present invention is effective in improving the strength and hydrophobicity of the nonwoven fabric.
Example 1 is different from comparative example 2 in that 1, 6-bis (acryloyloxy) -2,2,3,3,4,4,5, 5-octafluorohexane and pentaerythritol tetraacrylate were grafted on the surface of the nonwoven fabric through the step (5) in example 1, while comparative example 2 was not surface-grafted. Comparing the results of the tests in table 1, the nonwoven fabric made in example 1 was found to have significantly greater tensile strength and hydrostatic pressure than comparative example 2, indicating that surface grafting is effective in increasing the strength and hydrophobicity of the nonwoven fabric. The reason is presumed to be as follows: grafting two grafting monomers, namely 1, 6-bis (acryloyloxy) -2,2,3,3,4,4,5, 5-octafluorohexane and pentaerythritol tetraacrylate, onto the surface of the spunlace fiber web through carbon-carbon double bonds; meanwhile, a plurality of carbon-carbon double bonds exist in the two grafting monomers, and the carbon-carbon double bonds can generate photoinitiated polymerization reaction, so that a cross-linked network-shaped structure is formed on the surface of the spunlace fiber web, and the strength of the non-woven fabric is increased; meanwhile, the fluorine-containing group in the 1, 6-bis (acryloyloxy) -2,2,3,3,4,4,5, 5-octafluorohexane has better hydrophobicity, can form a hydrophobic interface on the surface of the non-woven fabric, and is not easy to fall off and has better durability because the hydrophobic interface is grafted on the surface of the non-woven fabric through a covalent bond.
Example 1 is different from comparative example 3 in that in example 1, a tris (hydroxymethyl) aminomethane-methyl acrylate-dipentaerythritol copolymer is added to the interior of the nonwoven fabric through steps (1) and (3), while in comparative example 3, the copolymer is not added. Comparing the test results of the two in table 1, it is found that the tensile strength of the nonwoven fabric prepared in example 1 is significantly greater than that of comparative example 3, indicating that the addition of the tris-hydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer is effective in improving the strength of the nonwoven fabric. The reason is presumed to be as follows: the trihydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer has a large number of terminal hydroxyl groups, and can form hydrogen bonds with free hydroxyl groups in cellulose fibers, so that more hydrogen bonds exist in a crosslinking area of the cellulose fibers, the crosslinking degree of the fibers is improved, and the strength of the non-woven fabric is increased; meanwhile, the terpolymer molecules have higher branching degree and can be crosslinked with cellulose fibers in all directions, so that the crosslinking degree of the fibers can be further improved, and the strength of the non-woven fabric is increased.
Example 1 is different from example 4 in that in example 4, a tris (hydroxymethyl) aminomethane-methyl acrylate-dipentaerythritol copolymer is bound to cellulose through a covalent bond through steps (2) and (4), whereas in example 1, the copolymer is bound to cellulose only through a hydrogen bond. Comparing the results of the tests in table 1, it was found that the nonwoven fabric obtained in example 4 had a significantly higher tensile strength than that of example 1. The reason is presumed to be as follows: in example 4, the tris-hydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer is grafted with carboxyl groups by the modification in step (2), and these carboxyl groups are esterified with hydroxyl groups in the cellulose fibers in step (2), and covalent crosslinks are formed between the terpolymer and the cellulose fibers, and the bonds of the covalent crosslinks are larger than those of hydrogen bonds, and are not easily broken, so that the strength of the nonwoven fabric can be further improved.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.

Claims (10)

1. The high-strength hydrophobic non-woven fabric is characterized by comprising the following raw materials in parts by weight: 100 parts of cellulose fiber, 5-10 parts of trihydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer, 30-35 parts of 1, 6-bis (acryloyloxy) -2,2,3,3,4,4,5, 5-octafluorohexane and 2-2.5 parts of pentaerythritol tetraacrylate.
2. The high-strength hydrophobic nonwoven fabric according to claim 1, wherein the method for preparing the tris-hydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer is as follows:
(i) addition reaction: adding trihydroxymethyl aminomethane into a methanol water solution, heating to 30-35 ℃, and stirring for dissolving; dropwise adding a methanol solution of methyl acrylate, and reacting for 2-3 h at the temperature of 30-35 ℃; after the reaction is finished, vacuumizing to remove methanol, water and excessive methyl acrylate to obtain an addition reaction product;
(ii) ester exchange reaction: adding dipentaerythritol into dimethyl sulfoxide, heating to 90-100 ℃, and stirring for dissolving; dropwise adding the addition reaction product obtained in the step (i), heating to 125-130 ℃, reacting for 2-3 h, and reacting for 1.5-2.5 h at 100-110 ℃ and 0.05-0.08 MPa; and after the reaction is finished, performing reduced pressure rotary evaporation to remove dimethyl sulfoxide to obtain the trihydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer.
3. The high-strength hydrophobic nonwoven fabric according to claim 2, wherein in the step (i), the mass ratio of the tris to the methyl acrylate is 1:1 to 1.5.
4. The high-strength hydrophobic nonwoven fabric according to claim 2, wherein the mass ratio of dipentaerythritol in step (ii) to tris in step (i) is 1:3.5 to 4.
5. The high-strength hydrophobic nonwoven fabric according to claim 1 or 2, wherein the tris-hydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer is a terpolymer modified by carboxyl grafting in the following way:
(a) ring opening reaction: dissolving a trihydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer in N, N-dimethylformamide, adding a ring-opening reaction catalyst, dropwise adding an N, N-dimethylformamide solution of 2-oxaproyl ethyl acetate, and reacting for 2-3 h at the temperature of 70-80 ℃; after the reaction is finished, carrying out reduced pressure distillation to remove the N, N-dimethylformamide and obtain a ring-opening reaction product;
(b) and (3) hydrolysis reaction: dissolving the ring-opening reaction product obtained in the step (a) in water, adding a sodium hydroxide solution, and reacting at 60-70 ℃ for 1-2 h; after the reaction is finished, the water is removed by reduced pressure distillation, and the terpolymer modified by carboxyl grafting is obtained.
6. The high-strength hydrophobic nonwoven fabric according to claim 5, wherein in the step (a), the mass ratio of the trihydroxymethylaminomethane-methyl acrylate-dipentaerythritol copolymer to the 2-oxaproyl ethyl acetate is 1: 1.5-2.
7. A method for preparing the high-strength hydrophobic nonwoven fabric as claimed in any one of claims 1 to 4, comprising the steps of:
(1) loosening cellulose fibers, and dispersing the loosened cellulose fibers in water to prepare a fiber suspension;
(2) mixing the fiber suspension with a trihydroxymethyl aminomethane-methyl acrylate-dipentaerythritol copolymer, and performing wet-laid to prepare a fiber web;
(3) carrying out spunlace reinforcement, washing and drying on the fiber web to obtain a spunlace fiber web;
(4) 1, 6-bis (acryloyloxy) -2,2,3,3,4,4,5, 5-octafluorohexane and pentaerythritol tetraacrylate are taken as grafting monomers, and ultraviolet surface grafting is carried out on the spunlace fiber web to obtain a fiber web subjected to grafting treatment;
(5) and cutting the grafted fiber web to obtain the high-strength hydrophobic non-woven fabric.
8. The method for preparing a high-strength hydrophobic nonwoven fabric according to claim 7, wherein in the step (4), the ultraviolet surface grafting method comprises the following steps: dissolving 1, 6-bis (acryloyloxy) -2,2,3,3,4,4,5, 5-octafluorohexane, pentaerythritol tetraacrylate and a photoinitiator in acetone to prepare a mixed solution; immersing the spunlace fiber web into the mixed solution, and carrying out grafting reaction under ultraviolet light; after the reaction, the spunlace fiber web is transferred into acetone, monomers and polymers which are not grafted to the spunlace fiber web are removed through ultrasonic treatment, and the monomers and polymers which are not grafted to the spunlace fiber web are further removed through acetone extraction.
9. A method for preparing the high-strength hydrophobic nonwoven fabric as claimed in any one of claims 5 to 6, comprising the steps of:
(1) loosening cellulose fibers, and dispersing the loosened cellulose fibers in water to prepare a fiber suspension;
(2) adding an esterification reaction catalyst into the fiber suspension, dropwise adding an aqueous solution of a carboxyl graft modified terpolymer under stirring, and reacting for 2-3 h at 80-85 ℃; after the reaction is finished, wet-laying to prepare a fiber web;
(3) carrying out spunlace reinforcement, washing and drying on the fiber web to obtain a spunlace fiber web;
(4) 1, 6-bis (acryloyloxy) -2,2,3,3,4,4,5, 5-octafluorohexane and pentaerythritol tetraacrylate are taken as grafting monomers, and ultraviolet surface grafting is carried out on the spunlace fiber web to obtain a fiber web subjected to grafting treatment;
(5) and cutting the grafted fiber web to obtain the high-strength hydrophobic non-woven fabric.
10. The method for preparing the high-strength hydrophobic nonwoven fabric according to claim 9, wherein in the step (4), the ultraviolet surface grafting method comprises the following steps: dissolving 1, 6-bis (acryloyloxy) -2,2,3,3,4,4,5, 5-octafluorohexane, pentaerythritol tetraacrylate and a photoinitiator in acetone to prepare a mixed solution; immersing the spunlace fiber web into the mixed solution, and carrying out grafting reaction under ultraviolet light; after the reaction, the spunlace fiber web is transferred into acetone, monomers and polymers which are not grafted to the spunlace fiber web are removed through ultrasonic treatment, and the monomers and polymers which are not grafted to the spunlace fiber web are further removed through acetone extraction.
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CN114016302A (en) * 2021-11-05 2022-02-08 福建百爵纸制品有限责任公司 Preparation method of pure cotton non-woven fabric with dry and comfortable surface finish, non-woven fabric and device

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