CN114737399B - Environment-friendly flame-retardant sizing formula for fabric - Google Patents
Environment-friendly flame-retardant sizing formula for fabric Download PDFInfo
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- CN114737399B CN114737399B CN202210532474.5A CN202210532474A CN114737399B CN 114737399 B CN114737399 B CN 114737399B CN 202210532474 A CN202210532474 A CN 202210532474A CN 114737399 B CN114737399 B CN 114737399B
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- hydrotalcite
- polyborosiloxane
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- reaction kettle
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000003063 flame retardant Substances 0.000 title claims abstract description 46
- 239000004744 fabric Substances 0.000 title claims abstract description 36
- 238000004513 sizing Methods 0.000 title claims abstract description 26
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 80
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 80
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 68
- 239000002131 composite material Substances 0.000 claims abstract description 33
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 26
- -1 hydrotalcite compound Chemical class 0.000 claims abstract description 14
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 229920000609 methyl cellulose Polymers 0.000 claims abstract description 7
- 239000001923 methylcellulose Substances 0.000 claims abstract description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 41
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 16
- 239000004327 boric acid Substances 0.000 claims description 16
- 229920002545 silicone oil Polymers 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 230000002687 intercalation Effects 0.000 claims description 5
- 238000009830 intercalation Methods 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 238000009472 formulation Methods 0.000 claims description 4
- 239000003377 acid catalyst Substances 0.000 claims description 3
- 239000010410 layer Substances 0.000 abstract description 14
- 230000004888 barrier function Effects 0.000 abstract description 10
- 239000000779 smoke Substances 0.000 abstract description 10
- 229910002923 B–O–B Inorganic materials 0.000 abstract description 9
- 229910002808 Si–O–Si Inorganic materials 0.000 abstract description 8
- 229910052796 boron Inorganic materials 0.000 abstract description 7
- 239000000919 ceramic Substances 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 239000011229 interlayer Substances 0.000 abstract description 6
- 231100000053 low toxicity Toxicity 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 16
- 230000006872 improvement Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 7
- 231100000419 toxicity Toxicity 0.000 description 6
- 230000001988 toxicity Effects 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 229920004933 Terylene® Polymers 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- CFOAUMXQOCBWNJ-UHFFFAOYSA-N [B].[Si] Chemical group [B].[Si] CFOAUMXQOCBWNJ-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/76—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon oxides or carbonates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
- D06M15/05—Cellulose or derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/53—Polyethers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/30—Flame or heat resistance, fire retardancy properties
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Silicon Polymers (AREA)
Abstract
The invention provides an environment-friendly flame-retardant sizing agent formula for fabrics, which comprises, by weight, 100 parts of polyborosiloxane grafted hydrotalcite composite, 40-60 parts of polyacrylamide, 1-3 parts of polyethylene glycol, 10-20 parts of methylcellulose and 10-30 parts of solvent. The invention takes polyborosiloxane grafted hydrotalcite compound and polyacrylamide as main components, the polyborosiloxane grafted hydrotalcite compound contains Si-O-Si, si-O-B and B-O-B bonds, the polyborosiloxane and the hydroxyl groups of hydrotalcite are condensed to realize grafting, and the hydrotalcite interlayer contains moisture and a large number of hydroxyl groups, so that the obtained compound is pyrolyzed to form high-stability bonding states of Si-O-Si, si-O-B, B-O-B and the like when being combusted, and simultaneously forms a compact composite ceramic barrier layer with grafted hydrotalcite, thereby realizing the purposes of quick flame retardance, low smoke and low toxicity.
Description
Technical Field
The invention relates to the technical field of flame-retardant sizing, in particular to an environment-friendly flame-retardant sizing formula for fabrics.
Background
Fabrics are closely related to the life of people, for example, are used in the fields of clothing, carpets, sofas and the like, so that the improvement of the flame retardance of the fabrics is of great significance in reducing the harm of fire disasters to human life. Flame retardant fabrics are fabrics that when contacted by a flame or hot object, prevent themselves from igniting or retarding and ending combustion. The flame retardance of the fabric can be realized by adding a flame retardant into the spinning solution or performing flame-retardant sizing after-finishing. The cost of after-finishing flame retardance is low, and the fabric also has flame retardance through the flame retardance effect of the flame retardant. The flame retardant performance of the after-finishing flame-retardant fabric depends on the flame retardant effect of the flame retardant, so that the flame retardant quality of the after-finishing flame-retardant fabric is directly determined. Patent CN201510337327.2 discloses an anti-dripping flame-retardant polyester fabric compound and a preparation method thereof, wherein the polyester fabric is padded in a flame-retardant additive and anti-dripping additive dispersion liquid to obtain the anti-dripping flame-retardant polyester fabric. Wherein the anti-dripping additive comprises a boron-containing auxiliary agent, a polyhydroxy compound capable of complexing with boron, a phosphorus-containing flame-retardant adhesive and an organosilicon crosslinking agent; the complex reaction of boron and polyhydroxy and the crosslinking reaction of organosilicon crosslinking agent and hydroxyl are utilized to lead the polyhydroxy compound to form a space network structure, and the polyhydroxy compound is tightly adhered to the surface of terylene by the phosphorus-containing adhesive. When encountering flame, the polyhydroxy compound is rapidly dehydrated into carbon under the multiple catalytic dehydration actions of the phosphorus-containing flame retardant, the phosphorus-containing adhesive and the flame-retardant terylene, and the polyhydroxy compound forms a space reticular carbon layer with compact structure, so that the flame retardant and the anti-dripping effect can be effectively realized. However, the combustion improver added with the phosphorus-containing combustion improver has the advantages of high volatility, poor heat resistance, unsatisfactory compatibility, and certain toxicity to human bodies due to the generation of dripping substances during combustion.
In view of the foregoing, there is a need for an improved environment-friendly flame-retardant sizing formulation for fabrics to solve the above-mentioned problems.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide an environment-friendly flame-retardant sizing agent formula for fabrics, which takes a polyborosiloxane grafted hydrotalcite compound and polyacrylamide as main components, wherein the polyborosiloxane grafted hydrotalcite compound has high flame retardance, can quickly form an inorganic oxygen-insulating heat-insulating protective layer during combustion, has low smoke toxicity, is environment-friendly, and is suitable for flame retardance of textiles.
The invention provides an environment-friendly flame-retardant sizing agent formula for fabrics, which comprises, by weight, 100 parts of polyborosiloxane grafted hydrotalcite composite, 40-60 parts of polyacrylamide, 1-3 parts of polyethylene glycol, 10-20 parts of methylcellulose and 10-30 parts of solvent.
As a further improvement of the invention, the addition amount of the polyacrylamide is 45-55 parts.
As a further improvement of the invention, the solvent is one or more of water, ethanol and acetone.
As a further improvement of the invention, the mass ratio of the polyborosiloxane to the hydrotalcite in the polyborosiloxane grafted hydrotalcite composite is 1: (0.2-0.5).
As a further improvement of the present invention, the polyborosiloxane is obtained by reacting methyltriethoxysilane, hydroxy silicone oil and boric acid.
As a further improvement of the invention, the mass ratio of methyltriethoxysilane, hydroxy silicone oil and boric acid is 1: (0.1-0.3): (0.3-0.6).
As a further improvement of the present invention, the preparation method of the polyborosiloxane grafted hydrotalcite composite comprises:
s1, placing hydrotalcite in a first-stage high-pressure reaction kettle, and introducing high-temperature high-pressure superheated steam to stay for 1-3min;
s2, adding methyltriethoxysilane, hydroxyl silicone oil and boric acid into the aqueous solution, and then placing the aqueous solution into a second-stage high-pressure reaction kettle;
s3, introducing the hydrotalcite treated in the step S1 into the second-stage high-pressure reaction kettle, and performing intercalation, grafting and polymerization reaction to obtain a polyborosiloxane grafted hydrotalcite compound; the temperature and the pressure of the second-stage high-pressure reaction kettle are lower than those of the first-stage high-pressure reaction kettle.
As a further improvement of the invention, the temperature of the first-stage high-pressure reaction kettle is 150-220 ℃ and the pressure is 1.5-2MPa; the temperature of the second-stage high-pressure reaction kettle is 70-90 ℃ and the pressure is 0.2-1MPa.
As a further improvement of the invention, the temperature of the first-stage high-pressure reaction kettle is 180-200 ℃ and the pressure is 1.6-1.8MPa; the temperature of the second-stage high-pressure reaction kettle is 80-90 ℃ and the pressure is 0.3-0.6MPa. As a further improvement of the present invention, the aqueous solution further comprises an acid catalyst.
The beneficial effects of the invention are as follows:
1. the environment-friendly flame-retardant sizing agent formula for fabrics provided by the invention takes the polyborosiloxane grafted hydrotalcite composite and polyacrylamide as main components, the polyborosiloxane grafted hydrotalcite composite contains Si-O-Si, si-O-B and B-O-B bonds, the polyborosiloxane and the hydroxyl groups of hydrotalcite are condensed to realize grafting, the hydrotalcite layers contain water and a large number of hydroxyl groups, and when the obtained composite is combusted, the polyborosiloxane is pyrolyzed to form high-stability bonding states such as Si-O-Si, si-O-B, B-O-B and the like, and meanwhile, the polyborosiloxane and the grafted hydrotalcite form a compact composite ceramic barrier layer, so that the purposes of quick flame retardance, low smoke and low toxicity are realized.
2. According to the environment-friendly flame-retardant sizing mixing formula for the fabric, hydrotalcite is permeated into the first-stage high-pressure reaction kettle from the layers of the hydrotalcite, when the hydrotalcite enters the second-stage high-pressure reaction kettle, due to the sudden drop of temperature and pressure, the instantaneous pressure release is realized, so that internal water vapor is released to form certain stripping to the hydrotalcite, meanwhile, methyltriethoxysilane, hydroxyl silicone oil and boric acid in the second-stage high-pressure reaction kettle enter the layers to perform polycondensation reaction, alkoxy and hydroxyl can be grafted with hydroxyl on the hydrotalcite, and the grafting rate of the polyborosiloxane grafted hydrotalcite compound is high, the interlayer spacing is increased, and the polyborosiloxane grafted hydrotalcite compound serving as a combustion improver has remarkable high barrier property.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to specific embodiments.
It should be further noted that, in order to avoid obscuring the present invention due to unnecessary details, only structures and/or processing steps closely related to aspects of the present invention are shown in the specific embodiments, and other details not greatly related to the present invention are omitted.
In addition, it should be further noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides an environment-friendly flame-retardant sizing formula for fabrics, which comprises, by weight, 100 parts of polyborosiloxane grafted hydrotalcite composite, 40-60 parts of polyacrylamide, 1-3 parts of polyethylene glycol, 10-20 parts of methylcellulose and 10-30 parts of solvent. Preferably, the addition amount of the polyacrylamide is 45-55 parts. Preferably, the composition comprises 100 parts by weight of polyborosiloxane grafted hydrotalcite composite, 45-55 parts by weight of polyacrylamide, 2-3 parts by weight of polyethylene glycol, 12-18 parts by weight of methylcellulose and 15-20 parts by weight of solvent.
The polyborosiloxane grafted hydrotalcite composite contains Si-O-Si, si-O-B and B-O-B bonds, grafting is realized by condensation of hydroxyl groups of polyborosiloxane and hydrotalcite, moisture and a large number of hydroxyl groups are contained between hydrotalcite layers, and when the obtained composite is burnt, polyborosiloxane is pyrolyzed to form high-stability bonding states of Si-O-Si, si-O-B, B-O-B and the like, and meanwhile, a composite ceramic barrier layer is formed with grafted hydrotalcite, so that the purposes of quick flame retardance, low smoke and low toxicity are realized.
The solvent is one or more of water, ethanol and acetone, preferably water.
The mass ratio of the polyborosiloxane to the hydrotalcite in the polyborosiloxane grafted hydrotalcite composite is 1: (0.2-0.5), preferably 1: (0.3-0.4). When the hydrotalcite content is too much, the uniformity and film forming property of the slurry are not improved, and the proper compounding ratio is beneficial to forming a ceramic barrier layer with high strength and compactness when the polyborosiloxane and the hydrotalcite are combusted.
The polyborosiloxane comprises the following components in percentage by mass: (0.1-0.3): (0.3-0.6), hydroxy silicone oil and boric acid. The mass ratio is preferably 1: (0.2-0.3): (0.4-0.5). A suitable amount of boric acid contributes to the formation of Si-O-B and B-O-B bonds.
The preparation method of the polyborosiloxane grafted hydrotalcite composite comprises the following steps:
s1, placing hydrotalcite in a first-stage high-pressure reaction kettle, and introducing high-temperature high-pressure superheated steam to stay for 1-3min; s2, adding methyltriethoxysilane, hydroxyl silicone oil and boric acid into the aqueous solution, and then placing the aqueous solution into a second-stage high-pressure reaction kettle; preferably, the aqueous solution further comprises an acid catalyst.
S3, introducing the hydrotalcite treated in the step S1 into the second-stage high-pressure reaction kettle, and performing intercalation, grafting and polymerization reaction to obtain a polyborosiloxane grafted hydrotalcite compound; the temperature and the pressure of the second-stage high-pressure reaction kettle are lower than those of the first-stage high-pressure reaction kettle.
In the first-stage high-pressure reaction kettle, high-temperature high-pressure superheated steam permeates into the interlayer of the hydrotalcite, when the hydrotalcite enters the second-stage high-pressure reaction kettle, due to sudden drop of temperature and pressure, instantaneous pressure release is realized, so that internal steam is released to form certain stripping on the hydrotalcite, methyl triethoxysilane, hydroxyl silicone oil and boric acid in the second-stage high-pressure reaction kettle enter the interlayer to perform polycondensation reaction, alkoxy and hydroxyl can be grafted with hydroxyl on the hydrotalcite, the grafting rate of the polyborosiloxane grafted hydrotalcite compound obtained in the way is high, the interlayer spacing is increased, and the polyborosiloxane grafted hydrotalcite compound has obvious high barrier property as a combustion improver.
The temperature of the first-stage high-pressure reaction kettle is 150-220 ℃ and the pressure is 1.5-2MPa; the temperature of the second-stage high-pressure reaction kettle is 70-90 ℃ and the pressure is 0.2-1MPa.
Preferably, the temperature of the first-stage high-pressure reaction kettle is 180-200 ℃ and the pressure is 1.6-1.8MPa; the temperature of the second-stage high-pressure reaction kettle is 80-90 ℃ and the pressure is 0.3-0.6MPa.
Example 1
The environment-friendly flame-retardant sizing agent formula for the fabric comprises, by weight, 100 parts of polyborosiloxane grafted hydrotalcite composite, 50 parts of polyacrylamide, 2.5 parts of polyethylene glycol, 15 parts of methylcellulose and 18 parts of solvent water. And mixing the components for size mixing, and then padding and sizing the cotton fabric to obtain the flame-retardant cotton fabric.
The preparation method of the polyborosiloxane grafted hydrotalcite composite comprises the following steps:
s1, placing hydrotalcite in a first-stage high-pressure reaction kettle, and introducing high-temperature high-pressure superheated steam to stay for 2min; the temperature of the first-stage high-pressure reaction kettle is 180 ℃ and the pressure is 1.8MPa;
s2, the mass ratio is 1:0.2:0.5 methyltriethoxysilane, hydroxy silicone oil and boric acid are added to the aqueous solution and then placed in a second-stage autoclave; the temperature of the second-stage high-pressure reaction kettle is 80 ℃ and the pressure is 0.5MPa. The total mass ratio of hydrotalcite to methyltriethoxysilane, hydroxy silicone oil and boric acid was 0.4:1.
S3, introducing the hydrotalcite treated in the step S1 into the second-stage high-pressure reaction kettle, and performing intercalation, grafting and polymerization reaction to obtain the polyborosiloxane grafted hydrotalcite composite.
Example 2
Compared with the example 1, the environment-friendly flame-retardant sizing formula for the fabric is characterized by comprising 100 parts by weight of polyborosiloxane grafted hydrotalcite composite, 40 parts by weight of polyacrylamide, 1 part by weight of polyethylene glycol, 10 parts by weight of methylcellulose and 12 parts by weight of solvent water. The other points are substantially the same as those of embodiment 1, and will not be described here again.
Comparative example 1
Compared with the example 1, the environment-friendly flame-retardant sizing formula for fabrics is different in that polyborosiloxane grafted hydrotalcite compound is replaced by polyborosiloxane and hydrotalcite which are not grafted. The other points are substantially the same as those of embodiment 1, and will not be described here again.
Comparative example 2
Compared with the example 1, the environment-friendly flame-retardant sizing formula for fabrics is characterized in that the preparation method of the polyborosiloxane grafted hydrotalcite composite comprises the following steps: the mass ratio is 1:0.2:0.5 methyltriethoxysilane, hydroxy silicone oil and boric acid were added to the aqueous solution, and hydrotalcite was then added thereto, and reacted at 80℃and normal pressure.
The other points are substantially the same as those of embodiment 1, and will not be described here again.
Comparative example 3
Compared with the example 1, the environment-friendly flame-retardant sizing formula for fabrics is characterized in that the preparation method of the polyborosiloxane grafted hydrotalcite composite comprises the following steps:
s1, placing hydrotalcite in a first-stage high-pressure reaction kettle, and introducing high-temperature high-pressure superheated steam to stay for 2min; the temperature of the first-stage high-pressure reaction kettle is 180 ℃ and the pressure is 1.8MPa;
s2, introducing the hydrotalcite treated in the step S1 into a second-stage high-pressure reaction kettle to stay for 20min, so as to obtain peeled hydrotalcite; the temperature of the second-stage high-pressure reaction kettle is 80 ℃ and the pressure is 0.5MPa;
s3, the mass ratio is 1:0.2:0.5 methyltriethoxysilane, hydroxy silicone oil and boric acid are added into an aqueous solution, then the peeled hydrotalcite obtained in the step S2 is added, and the polyborosiloxane grafted hydrotalcite composite is obtained through polycondensation and grafting.
The other points are substantially the same as those of embodiment 1, and will not be described here again.
Comparative example 4
Compared with the example 1, the environment-friendly flame-retardant sizing formula for the fabric is different in that boric acid is not added in the step S2. The other points are substantially the same as those of embodiment 1, and will not be described here again.
Comparative example 5
Compared with the example 1, the environment-friendly flame-retardant sizing formula for fabrics is different in that the polyborosiloxane grafted hydrotalcite compound is replaced by polyborosiloxane. The other points are substantially the same as those of embodiment 1, and will not be described here again.
TABLE 1 test results for examples 1-2 and comparative examples 1-5
| Sample preparation | Limiting oxygen index (%) | Smoke density grade | Grade of tobacco toxicity |
| Example 1 | 35.6 | 9.8 | AQ2 |
| Example 2 | 35.1 | 10.1 | AQ2 |
| Comparative example 1 | 32.5 | 11.2 | ZA1 |
| Comparative example 2 | 33.6 | 10.8 | ZA1 |
| Comparative example 3 | 33.8 | 10.5 | AQ2 |
| Comparative example 4 | 33.3 | 10.8 | AQ2 |
| Comparative example 5 | 30.1 | 12.3 | ZA1 |
As can be seen from Table 1, the sizing formula of the invention can obviously improve the limiting oxygen index of the fabric, and has low smoke density and toxicity, thus having high safety and good flame retardant effect. In contrast, when the polyborosiloxane and hydrotalcite are not grafted in the comparative example 1, the limiting oxygen index is reduced, the smoke density grade is increased, and the smoke toxicity is improved, so that the invention facilitates forming a composite ceramic barrier layer by grafting the polyborosiloxane and hydrotalcite, improves the heat insulation flame retardance, further reduces the release amount of smoke and improves the structure of a release object, thereby reducing the toxicity. The conventional grafting polymerization method is adopted in the comparative example 2, and the flame retardant effect is not as good as that of the invention, and the special steam explosion intercalation and grafting are adopted, so that the grafting rate and grafting uniformity are improved, and simultaneously, the polyborosiloxane is inserted between layers, and the compactness of the barrier layer is improved. In comparative example 3, the flame retardant effect was similarly reduced by blasting and peeling followed by graft polymerization. When no boric acid was added in comparative example 4, the flame retardant effect was also reduced, indicating that the silicon-boron chains help to improve the flame retardancy of the composite. When hydrotalcite is not added in comparative example 5, the flame retardant effect is remarkably reduced, which shows that the composition of polyborosiloxane and hydrotalcite is favorable for forming a compact barrier ceramic layer, thereby realizing high-efficiency flame retardance.
In summary, the environment-friendly flame-retardant sizing agent formula for fabrics provided by the invention takes the polyborosiloxane grafted hydrotalcite composite and polyacrylamide as main components, the polyborosiloxane grafted hydrotalcite composite contains Si-O-Si, si-O-B and B-O-B bonds, the polyborosiloxane and the hydroxyl groups of hydrotalcite are condensed to realize grafting, and the hydrotalcite interlayer contains moisture and a large number of hydroxyl groups, so that the obtained composite has high-stability bonding states such as Si-O-Si, si-O-B, B-O-B and the like by pyrolysis of the polyborosiloxane when the composite is combusted, and simultaneously forms a compact composite ceramic barrier layer with grafted hydrotalcite, thereby achieving the purposes of rapid flame retardance, low smoke and low toxicity.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention.
Claims (4)
1. The environment-friendly flame-retardant sizing agent formula for fabrics is characterized by comprising, by weight, 100 parts of a polyborosiloxane grafted hydrotalcite composite, 40-60 parts of polyacrylamide, 1-3 parts of polyethylene glycol, 10-20 parts of methylcellulose and 10-30 parts of a solvent, wherein the mass ratio of polyborosiloxane to hydrotalcite in the polyborosiloxane grafted hydrotalcite composite is 1 (0.2-0.5), and the preparation method of the polyborosiloxane grafted hydrotalcite composite comprises the following steps:
s1, placing hydrotalcite in a first-stage high-pressure reaction kettle, and introducing high-temperature high-pressure superheated steam to stay for 1-3min;
s2, adding methyltriethoxysilane, hydroxyl silicone oil and boric acid into an aqueous solution, and then placing the aqueous solution into a second-stage high-pressure reaction kettle, wherein the mass ratio of the methyltriethoxysilane to the hydroxyl silicone oil to the boric acid is 1: (0.1-0.3): (0.3-0.6);
s3, introducing the hydrotalcite treated in the step S1 into the second-stage high-pressure reaction kettle to perform intercalation, grafting and polymerization reaction to obtain a polyborosiloxane grafted hydrotalcite compound; the temperature and the pressure of the second-stage high-pressure reaction kettle are lower than those of the first-stage high-pressure reaction kettle, the temperature of the first-stage high-pressure reaction kettle is 180-200 ℃, and the pressure is 1.6-1.8MPa; the temperature of the second-stage high-pressure reaction kettle is 80-90 ℃ and the pressure is 0.3-0.6MPa.
2. The environment-friendly flame-retardant sizing formulation for fabrics according to claim 1, wherein the addition amount of the polyacrylamide is 45-55 parts.
3. The environment-friendly flame-retardant sizing formulation for fabrics according to claim 1, wherein the solvent is one or more of water, ethanol and acetone.
4. The environmentally friendly flame retardant sizing formulation for fabrics according to claim 1, wherein said aqueous solution further comprises an acid catalyst.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US11094933B2 (en) * | 2016-07-18 | 2021-08-17 | University Of Kentucky Research Foundation | Polysiloxane binders |
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