CN117188040A - Organosilicon modified starch glass fiber cotton and preparation method and application thereof - Google Patents
Organosilicon modified starch glass fiber cotton and preparation method and application thereof Download PDFInfo
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- CN117188040A CN117188040A CN202311160409.5A CN202311160409A CN117188040A CN 117188040 A CN117188040 A CN 117188040A CN 202311160409 A CN202311160409 A CN 202311160409A CN 117188040 A CN117188040 A CN 117188040A
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- modified starch
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- fiber cotton
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- 229920000881 Modified starch Polymers 0.000 title claims abstract description 189
- 239000004368 Modified starch Substances 0.000 title claims abstract description 165
- 235000019426 modified starch Nutrition 0.000 title claims abstract description 159
- 239000003365 glass fiber Substances 0.000 title claims abstract description 149
- 229920000742 Cotton Polymers 0.000 title claims abstract description 129
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000853 adhesive Substances 0.000 claims abstract description 92
- 230000001070 adhesive effect Effects 0.000 claims abstract description 92
- 229920002472 Starch Polymers 0.000 claims abstract description 39
- 235000019698 starch Nutrition 0.000 claims abstract description 37
- 239000008107 starch Substances 0.000 claims abstract description 37
- 238000005406 washing Methods 0.000 claims abstract description 35
- 239000002356 single layer Substances 0.000 claims abstract description 21
- 238000009413 insulation Methods 0.000 claims abstract description 8
- 238000004321 preservation Methods 0.000 claims abstract description 5
- 238000001029 thermal curing Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 92
- 239000002994 raw material Substances 0.000 claims description 45
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 229920002261 Corn starch Polymers 0.000 claims description 35
- 239000008120 corn starch Substances 0.000 claims description 35
- 239000004094 surface-active agent Substances 0.000 claims description 35
- 239000005871 repellent Substances 0.000 claims description 34
- 230000002940 repellent Effects 0.000 claims description 33
- 239000002904 solvent Substances 0.000 claims description 32
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 29
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000003431 cross linking reagent Substances 0.000 claims description 27
- 229910052710 silicon Inorganic materials 0.000 claims description 27
- 239000010703 silicon Substances 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 24
- 239000002480 mineral oil Substances 0.000 claims description 23
- 235000010446 mineral oil Nutrition 0.000 claims description 23
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 19
- 239000010410 layer Substances 0.000 claims description 17
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 16
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 16
- 229920000570 polyether Polymers 0.000 claims description 16
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 15
- 230000002209 hydrophobic effect Effects 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 229920002545 silicone oil Polymers 0.000 claims description 15
- 229920001296 polysiloxane Polymers 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 11
- 229940126062 Compound A Drugs 0.000 claims description 10
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 10
- 238000001723 curing Methods 0.000 claims description 10
- 238000010526 radical polymerization reaction Methods 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 8
- -1 siloxane functional groups Chemical group 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 229920003180 amino resin Polymers 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000003595 mist Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 3
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 2
- KWXICGTUELOLSQ-UHFFFAOYSA-N 4-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=C(S(O)(=O)=O)C=C1 KWXICGTUELOLSQ-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 244000017020 Ipomoea batatas Species 0.000 claims description 2
- 235000002678 Ipomoea batatas Nutrition 0.000 claims description 2
- 240000003183 Manihot esculenta Species 0.000 claims description 2
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 2
- 240000004922 Vigna radiata Species 0.000 claims description 2
- 235000010721 Vigna radiata var radiata Nutrition 0.000 claims description 2
- 235000011469 Vigna radiata var sublobata Nutrition 0.000 claims description 2
- 238000007171 acid catalysis Methods 0.000 claims description 2
- 239000003377 acid catalyst Substances 0.000 claims description 2
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims description 2
- 239000007822 coupling agent Substances 0.000 claims description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 2
- 238000006266 etherification reaction Methods 0.000 claims description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical compound N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 claims description 2
- 239000012774 insulation material Substances 0.000 claims description 2
- 239000013067 intermediate product Substances 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920001592 potato starch Polymers 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- 229940100445 wheat starch Drugs 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 238000007039 two-step reaction Methods 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 33
- 239000008367 deionised water Substances 0.000 description 29
- 229910021641 deionized water Inorganic materials 0.000 description 29
- 239000000047 product Substances 0.000 description 16
- BNCADMBVWNPPIZ-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCN(COC)C1=NC(N(COC)COC)=NC(N(COC)COC)=N1 BNCADMBVWNPPIZ-UHFFFAOYSA-N 0.000 description 12
- 239000011521 glass Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 229920001187 thermosetting polymer Polymers 0.000 description 11
- 238000005303 weighing Methods 0.000 description 10
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 9
- 238000009472 formulation Methods 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 210000002268 wool Anatomy 0.000 description 4
- 239000000835 fiber Substances 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 239000011491 glass wool Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- FKXISKWWZKRPED-UHFFFAOYSA-N C(CCC)ONC1(N(C(N(C(=N1)N)OCCCC)(N(C)OCCCC)OCCCC)OCCCC)OCCCC Chemical compound C(CCC)ONC1(N(C(N(C(=N1)N)OCCCC)(N(C)OCCCC)OCCCC)OCCCC)OCCCC FKXISKWWZKRPED-UHFFFAOYSA-N 0.000 description 1
- YGCOKJWKWLYHTG-UHFFFAOYSA-N [[4,6-bis[bis(hydroxymethyl)amino]-1,3,5-triazin-2-yl]-(hydroxymethyl)amino]methanol Chemical compound OCN(CO)C1=NC(N(CO)CO)=NC(N(CO)CO)=N1 YGCOKJWKWLYHTG-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000227 bioadhesive Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 125000003147 glycosyl group Chemical group 0.000 description 1
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- 239000000758 substrate Substances 0.000 description 1
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- 229920001059 synthetic polymer Polymers 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
Abstract
The invention discloses an organosilicon modified starch glass fiber cotton, a preparation method and application thereof, which are based on the advantages of environmental protection, biodegradability and the like of starch. The organosilicon modified starch adhesive is uniformly sprayed on the surface of single-layer glass fiber cotton, and the organosilicon modified starch glass fiber cotton is prepared after thermal curing, so that the organosilicon modified starch glass fiber cotton has excellent heat preservation and insulation properties, biodegradability, hydrophobicity, quality washing resistance and the like, and has wide application prospects in the fields of heat preservation, heat insulation, sound insulation and the like of buildings, automobiles and household appliances.
Description
Technical Field
The invention relates to the technical field of environment-friendly degradable glass fiber cotton, in particular to organic silicon modified starch glass fiber cotton and a preparation method and application thereof.
Background
The glass fiber cotton product is a high-performance heat-insulating material prepared from glass fibers and is widely applied to the fields of building, aerospace, automobiles, electronics, chemical industry and the like. In order to improve the hydrophobicity and lower the quality washing rate of the glass fiber cotton product, a specific adhesive is generally required to be added into the glass fiber cotton product, and the specific adhesive is used for improving the bundling property of the fiber, thereby improving the fiber strength, the hydrophobicity, the abrasion resistance and the softness. Natural adhesives are favored by researchers as a renewable resource, especially adhesives made of starch.
In recent years, the industrial production of adhesives has been advanced to low cost and zero pollution, and starch adhesives are used as natural renewable adhesives, so that the starch adhesives are superior to other adhesives in various aspects. However, formaldehyde is introduced into many existing adhesives, so that formaldehyde residues are generated in the products, certain harm is caused to the environment and human bodies, the production environment is deteriorated, and in addition, the water resistance, the bonding strength and the like of the adhesives are not ideal, so that the application is limited to a certain extent. In the research of modified starch, artificial synthetic polymers are mainly added at present, so that the process is complex and the cost is high.
Therefore, it is necessary to provide a novel formaldehyde-free, green and environment-friendly starch adhesive with good bonding strength, high drying speed and stable performances, which is used for producing glass fiber cotton, and can improve the problems of low hydrophobicity, low quality washing rate, mechanical properties and the like in the production of the starch glass fiber cotton, and has wide application prospect.
Disclosure of Invention
The invention aims to solve the problems that: the natural starch glass fiber cotton product has the problems of low hydrophobic rate, high quality washing rate, poor mechanical property and the like.
In order to solve the problems, the invention provides an organosilicon modified starch glass fiber cotton, which is prepared by the following steps: uniformly spraying an organosilicon modified starch adhesive on the surface of glass fiber, and performing high-temperature thermal curing to obtain organosilicon modified starch glass fiber cotton; the organosilicon modified starch adhesive is prepared by uniformly stirring organosilicon modified starch A, a surfactant B, a water repellent C, modified mineral oil D, a cross-linking agent E, a catalyst F and a solvent G according to a certain proportion; the organosilicon modified starch A endows starch with excellent hydrophobicity, is a polymer of random or block organosilicon modified starch synthesized by an organosilicon containing unsaturated double bonds and starch containing unsaturated double bonds in a free radical polymerization mode, and simultaneously reacts with hydroxyl groups on the surface of glass fibers by using siloxane functional groups of the polymer as a coupling agent, so that the starch and the glass fibers are chemically connected, and the organosilicon modified starch glass fiber cotton has excellent hydrophobicity, quality washing resistance and mechanical properties, and is a main technical innovation of the invention.
Further, the specific preparation method of the organosilicon modified starch A comprises the following steps: by starch A 1 Compound A containing unsaturated double bond modified and grafted by medium hydroxyl functional group 2 Then with organic silicon A containing unsaturated double bond 3 Free radical polymerization is carried out, and its typical molecular structural formula is as follows:
the number average molecular weight of the organosilicon modified starch is 23000-1000000, preferably 40000-300000, wherein x is the polymerization degree of glucose in the starch, y is the polymerization degree of unsaturated double bond modified starch, and z is the polymerization degree of unsaturated double bond containing organosilicon;
starch A 1 Is one or more of corn starch, mung bean starch, wheat starch, sweet potato starch and tapioca starch, and has hydroxyl functional group in molecular structure and unsaturated double bond-containing compound A 2 Grafting reaction, and simultaneously, participating in crosslinking curing reaction with a crosslinking agent in the organosilicon modified starch adhesive; in addition, starch A 1 The biodegradability of the organosilicon modified starch glass fiber cotton is endowed.
Compound A containing unsaturated double bond 2 Wherein R is 1 Is H or CH 3 ，A 2 Is one or more of N-methylolacrylamide, N-methylolmethacrylamide, acryloyl chloride, methacryloyl chloride and maleic anhydride, and is structurally characterized in that hydroxyl in the molecular structure is mixed with starch A under the acid catalysis condition 1 Etherification reaction of hydroxyl in molecular structure, starch A 1 The hydroxyl groups in the molecular structure will esterify the grafted acrylate.
Organosilicon A containing unsaturated double bonds 3 Wherein R is 2 Is H or CH 3 ，R 3 Is an alkane chain with 1-10 carbon atoms, A 3 Is a mixture of one or more compounds containing unsaturated double bonds; organosilicon A containing unsaturated double bonds 3 Improves the hydrophobicity of the starch, realizes the chemical connection of the starch and the glass fiber, and can improve the hydrophobicity, the quality washing resistance and the mechanical property of the starch glass fiber cotton.
Finally, in the free radical polymerization process of the organosilicon modified starch, an initiator A is added 4 And surfactant A 5 The initiator A 4 Ammonium persulfate as surfactant A 5 Sodium dodecyl sulfonate and NP-10One or two kinds of the components are mixed.
Further, the organic silicon modified starch A comprises the following raw materials in parts by weight: starch A 1 100 parts of unsaturated double bond-containing compound A 2 10-125 parts of organic silicon A containing unsaturated double bonds 3 50 to 1500 parts of initiator A 4 1-30 parts of surfactant A 5 10-80 parts.
The organosilicon modified starch A is prepared by two steps of reactions: first, starch A 1 And a compound A containing unsaturated double bonds 2 The intermediate product is synthesized by reacting an acid catalyst in a solution at 60-120 ℃ for 1-10 hours, and is called P0; second P0 and organosilicon A containing unsaturated double bonds 3 Proportionally adding initiator A 4 And surfactant A 5 The organosilicon modified starch A is prepared by a free radical polymerization mode, the solution polymerization temperature is 60-95 ℃, and the reaction time is 2-10h.
The surfactant B is one or more of siloxane, polyether modified siloxane and fluorocarbon siloxane, preferably polyether siloxane, the average molecular weight of which is 3000-200000, and the mass percentage of the siloxane chain segment and the polyether chain segment is 25-100%.
The water repellent C is silicone oil with average molecular weight of 5000-250000 and viscosity of 100CPS-1000CPS, preferably German Wake brand silicone oil.
The viscosity of the modified mineral oil D is 800 CPS-60000 CPS, preferably the modified mineral oil LD-702 of the fuel brand of the gallery is prepared by mixing industrial white oil, higher fatty glyceride, flatting agent and surfactant according to a certain proportion.
The cross-linking agent E is a compound which can be chemically cross-linked with hydroxyl functional groups in the molecular structure of the organosilicon modified starch and is one or more of polyfunctional isocyanate compounds, glycoluril resins, phenolic resins and amino resins; preferably amino resin, which may be one or more of hexamethylol melamine, hexamethoxy methyl melamine, hexabutoxy methyl melamine.
The catalyst F is an acidic compound for promoting the crosslinking reaction of the crosslinking agent and the organosilicon modified starch under the high-temperature condition, and can be one or more of p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, p-dodecylbenzenesulfonic acid and perfluorooctane sulfonic acid.
Solvent G is the primary medium for the silicone modified starch binder and may be a mixture of one or more of an alcoholic organic solvent and water, preferably water.
Further, the organosilicon modified starch adhesive comprises the following components in percentage by weight: 1 to 20 percent of organosilicon modified starch A, 0.001 to 1 percent of surfactant B, 0.5 to 20 percent of water repellent C, 0.1 to 1 percent of modified mineral oil D, 0.08 to 10 percent of cross-linking agent E, 0.01 to 0.2 percent of catalyst F and 80 to 95 percent of solvent G.
The preparation method of the organosilicon modified starch adhesive comprises the following steps: and uniformly mixing the organosilicon modified starch A, the surfactant B, the water repellent C, the modified mineral oil D, the cross-linking agent E, the catalyst F and the solvent G, stirring for 10-20min, and then standing for 1h to prepare the organosilicon modified starch adhesive.
The specific preparation method of the organic silicon modified starch glass fiber cotton comprises the following steps: spraying the organosilicon modified starch adhesive to the surface of the single-layer glass fiber cotton in mist droplets to obtain the organosilicon modified starch adhesive single-layer glass fiber cotton; and preparing blocky glass fiber cotton by paving the organosilicon modified starch adhesive single-layer glass fiber cotton layer by layer; finally, shaping by a clamp, and curing at a high temperature in an oven at 120-260 ℃ for 30-200min to prepare the organosilicon modified starch glass fiber cotton.
The usage amount of the organosilicon modified starch adhesive is generally 0.001% -15% of the mass of the glass fiber cotton substrate, and the organosilicon modified starch adhesive is uniformly sprayed on the surface of the glass fiber, so that the macromolecular adhesive is uniformly coated on each fiber, the hydrophobicity of the glass fiber cotton is improved, the quality washing rate is reduced, the recovery rate of the glass fiber cotton is improved by utilizing the degradable characteristic of biological glycosyl, and the environment-friendly development is met.
The organosilicon modified starch glass fiber cotton prepared by the method has the hydrophobicity ratio of more than 98 percent and the mass washing ratio of less than 5 percent, and is applied to heat preservation, heat insulation and sound insulation materials in the fields of construction, automobiles, household appliances, electronics and chemical industry.
The implementation of the invention has the following beneficial effects:
1. the organic silicon modified starch glass fiber cotton prepared by the method has the advantages of low dust rate, no burrs of glass fibers, good mechanical property, water repellency of more than 98 percent and quality washing rate of less than 5 percent, and has environmental protection and biodegradability, can be applied to the fields of heat preservation, heat insulation, sound insulation and the like in the fields of buildings, automobiles, household appliances, electronics, chemical industry and the like, and has wide application prospect.
2. The organosilicon modified starch adhesive is used for the surface treatment of glass fiber cotton, so that the flexibility of the glass fiber is improved, and the abrasion, broken filaments and burrs of the glass fiber in the production process can be effectively reduced; the glass fiber cotton has the advantages of excellent properties of the traditional glass fiber cotton, such as excellent insulating property, heat insulation property, corrosion resistance and the like, and also has the characteristics of reproducibility and degradability, and has important significance for popularization and sustainable development and environmental protection economy.
3. The organosilicon modified starch adhesive provided by the invention can effectively improve the degradability of the adhesive and the coupling grafting of the surface of glass fiber, and meanwhile, because the organosilicon modified starch has a hydrophobic chain segment through free radical polymerization, the organosilicon modified starch is matched with silicone oil and mineral oil, so that the adhesive is uniformly spread on the surface of the glass fiber, the flexibility of the glass fiber is improved, the friction effect among the glass fibers is reduced, the hydrophobic rate of glass fiber cotton is improved, the quality washing rate is reduced, and the mechanical property is improved.
Drawings
In order to more clearly illustrate the invention or the technical solutions of the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings can be obtained from them without inventive effort for a person skilled in the art.
FIG. 1 is a photograph of the silicone modified starch adhesive prepared in example 1;
FIG. 2 is a photograph of glass fiber wool after being heat-set in example 1;
FIG. 3 is a photograph of the glass wool of comparative example 1 after being heat-set;
FIG. 4 is a graph showing an experimental example of testing the mass washing rate of glass fiber wool;
fig. 5 is a graph showing an experimental example of testing the hydrophobicity of glass fiber wool.
Detailed Description
The following description of the embodiments of the present invention will be made more apparent and fully hereinafter with reference to the accompanying drawings, in which some, but not all embodiments of the invention are shown. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides organic silicon modified starch glass fiber cotton, which is prepared by the following steps: spraying the organosilicon modified starch adhesive to the surface of the single-layer glass fiber cotton in mist droplets to obtain the organosilicon modified starch adhesive single-layer glass fiber cotton; and preparing blocky glass fiber cotton by paving the organosilicon modified starch adhesive single-layer glass fiber cotton layer by layer; finally, shaping by a clamp, and curing at a high temperature in an oven at 120-260 ℃ for 30-200min to prepare the organosilicon modified starch glass fiber cotton.
The technical scheme of the present invention is described in detail below by specific example 1 and comparative examples 1 to 10:
example 1
The raw materials, the dosage and the preparation method for preparing the organosilicon modified starch in the embodiment are as follows: firstly, 9.9g of corn starch is weighed and added into a reaction device, and then 30g of deionized water is added, so that the corn starch is uniformly dispersed in water; adding 9.9-g N-methylol acrylamide and 0.2g of catalyst p-toluenesulfonic acid, and then starting a stirrer to enable the mixed solution to react for 2 hours at 90 ℃; after the reaction is completed, the reaction device is cooled at room temperature to obtain P0; weighing P0 with the solid content of 1.6g, NP-10 with the solid content of 0.5g and sodium dodecyl sulfonate with the solid content of 0.5g, dissolving in deionized water with the solid content of 27.67g, adding the mixture and 3- (methacryloyloxy) propyl trimethoxysilane with the solid content of 10g into a reaction device, uniformly stirring, adding ammonium persulfate with the solid content of 0.16g into the solution, and reacting for 8 hours at 70 ℃ to obtain the organosilicon modified starch A.
Then, the raw materials and the method for preparing the organosilicon modified starch adhesive are as follows: silicone modified starch a7.7G, surfactant B (polyether modified siloxane) 0.1G, water repellent C (wark silicone oil) 8.8G, modified mineral oil D0.4G, cross-linking agent E (hexamethoxymethyl melamine) 0.4G, catalyst F (p-toluene sulfonic acid) 0.1G, solvent G (deionized water 147.3G and n-propanol 35.2G). 8.8g of water repellent is added into 35.2g of n-propanol solvent, and the mixture is added into 147.3g of water together with other raw materials, and finally the mixture is uniformly stirred to obtain the organosilicon modified starch adhesive, as shown in figure 1.
Finally, 200g of the organosilicon modified starch adhesive is uniformly sprayed on a single layer with the thickness of 0.6-0.8mm and the size of 12x12cm 2 And 20 layers of glass fiber cotton are sprayed and paved in sequence and fixed by a glass plate, wherein the thickness of the glass fiber cotton is 25mm. And (3) placing the fixed glass fiber cotton into an oven, and performing thermosetting at 240 ℃ for 2 hours, as shown in figure 2, to obtain a glass fiber cotton product.
Comparative example 1
The raw materials, the dosage and the preparation method for preparing the organosilicon modified starch in the comparative example are as follows: firstly, 9.9g of corn starch is weighed and added into a reaction device, and then 30g of deionized water is added, so that the corn starch is uniformly dispersed in water; adding 9.9-g N-methylol acrylamide and 0.2g of catalyst p-toluenesulfonic acid, and then starting a stirrer to enable the mixed solution to react for 2 hours at 90 ℃; after the reaction is completed, the reaction device is cooled at room temperature to obtain P0; weighing and dissolving 1.6g of P0, 0.5g of NP-10 and 0.5g of sodium dodecyl sulfonate in 27.67g of deionized water, adding the sodium dodecyl sulfonate and 10g of 3- (methacryloyloxy) propyl trimethoxy silane into a reaction device, stirring uniformly, adding 0.16g of ammonium persulfate into the solution, and reacting for 8 hours at 70 ℃ to obtain the organosilicon modified starch A.
Then, the raw materials and the method for preparing the organosilicon modified starch adhesive are as follows: silicone modified starch a7.7G, surfactant B (polyether modified siloxane) 0.1G, water repellent C (wark silicone oil) 8.8G, modified mineral oil D0.4G, cross-linking agent E (hexamethoxymethyl melamine) 0.4G, catalyst F (p-toluene sulfonic acid) 0.1G, solvent G (deionized water 147.3G and n-propanol 35.2G). 8.8g of water repellent is added into 35.2g of normal propyl alcohol solvent, and is added into 147.3g of water together with the other raw materials, and finally the organosilicon modified starch adhesive is obtained after uniform stirring.
Finally, 150g of the organosilicon modified starch adhesive is uniformly sprayed on a single layer with the thickness of 0.6-0.8mm and the size of 12x12cm 2 And 20 layers of glass fiber cotton are sprayed and paved in sequence, and the glass fiber cotton is fixed by a glass plate, wherein the thickness of the glass fiber cotton is 25mm. And (3) placing the fixed glass fiber cotton into an oven, and performing thermosetting at 240 ℃ for 2 hours to obtain a glass fiber cotton product, as shown in figure 3.
Comparative example 2
The raw materials, the dosage and the preparation method for preparing the organosilicon modified starch in the comparative example are as follows: firstly, 9.9g of corn starch is weighed and added into a reaction device, and then 30g of deionized water is added, so that the corn starch is uniformly dispersed in water; adding 9.9-g N-methylol acrylamide and 0.2g of catalyst p-toluenesulfonic acid, and then starting a stirrer to enable the mixed solution to react for 2 hours at 90 ℃; after the reaction is completed, the reaction device is cooled at room temperature to obtain P0; weighing and dissolving 1.6g of P0, 0.5g of NP-10 and 0.5g of sodium dodecyl sulfonate in 27.67g of deionized water, adding the sodium dodecyl sulfonate and 10g of 3- (methacryloyloxy) propyl trimethoxy silane into a reaction device, stirring uniformly, adding 0.16g of ammonium persulfate into the solution, and reacting for 8 hours at 70 ℃ to obtain the organosilicon modified starch A.
Then, the raw materials and the method for preparing the organosilicon modified starch adhesive are as follows: silicone modified starch a7.7G, surfactant B (polyether modified siloxane) 1G, water repellent C (wark silicone oil) 8.8G, modified mineral oil D0.4G, cross-linking agent E (hexamethoxymethyl melamine) 0.4G, catalyst F (p-toluene sulfonic acid) 0.1G, solvent G (deionized water 146.4G and n-propanol 35.2G). 8.8g of water repellent is added into 35.2g of normal propyl alcohol solvent, and is added into 146.4g of water together with the other raw materials, and finally the organosilicon modified starch adhesive is obtained after uniform stirring.
Finally, 200g of the organosilicon modified starch adhesive is uniformly sprayed on a single layer with the thickness of 0.6-0.8mm and the size of 12x12cm 2 And 20 layers of glass fiber cotton are sprayed and paved in sequence, and the glass fiber cotton is fixed by a glass plate, wherein the thickness of the glass fiber cotton is 25mm. And (3) placing the fixed glass fiber cotton into an oven, and performing thermosetting at 240 ℃ for 2 hours to obtain a glass fiber cotton product.
Comparative example 3
The raw materials, the dosage and the preparation method for preparing the organosilicon modified starch in the comparative example are as follows: firstly, 9.9g of corn starch is weighed and added into a reaction device, and then 30g of deionized water is added, so that the corn starch is uniformly dispersed in water; adding 9.9-g N-methylol acrylamide and 0.2g of catalyst p-toluenesulfonic acid, and then starting a stirrer to enable the mixed solution to react for 2 hours at 90 ℃; after the reaction is completed, the reaction device is cooled at room temperature to obtain P0; weighing and dissolving 1.6g of P0, 0.5g of NP-10 and 0.5g of sodium dodecyl sulfonate in 27.67g of deionized water, adding the sodium dodecyl sulfonate and 10g of 3- (methacryloyloxy) propyl trimethoxy silane into a reaction device, stirring uniformly, adding 0.16g of ammonium persulfate into the solution, and reacting for 8 hours at 70 ℃ to obtain the organosilicon modified starch A.
Then, the raw materials and the method of the organosilicon modified starch adhesive are as follows: silicone modified starch a7.7G, surfactant B (polyether modified siloxane) 0.1G, water repellent C (wark silicone oil) 8.8G, modified mineral oil D0.4G, cross-linking agent E (hexamethoxymethyl melamine) 5.2G, catalyst F (p-toluene sulfonic acid) 0.1G, solvent G (deionized water 142.5G and n-propanol 35.2G). 8.8g of water repellent is added into 35.2g of normal propyl alcohol solvent, and is added into 142.5g of water together with the other raw materials, and finally the organosilicon modified starch adhesive is obtained after uniform stirring.
Finally, the above organic silicon is modified200g of starch adhesive is uniformly sprayed on a single layer with the thickness of 0.6-0.8mm and the size of 12x12cm 2 And 20 layers of glass fiber cotton are sprayed and paved in sequence, and the glass fiber cotton is fixed by a glass plate, wherein the thickness of the glass fiber cotton is 25mm. And (3) placing the fixed glass fiber cotton into an oven, and performing thermosetting at 240 ℃ for 2 hours to obtain a glass fiber cotton product.
Comparative example 4
The raw materials, the dosage and the preparation method for preparing the organosilicon modified starch in the comparative example are as follows: firstly, 9.9g of corn starch is weighed and added into a reaction device, and then 30g of deionized water is added, so that the corn starch is uniformly dispersed in water; adding 9.9-g N-methylol acrylamide and 0.2g of catalyst p-toluenesulfonic acid, and then starting a stirrer to enable the mixed solution to react for 2 hours at 90 ℃; after the reaction is completed, the reaction device is cooled at room temperature to obtain P0; weighing and dissolving 1.6g of P0, 0.5g of NP-10 and 0.5g of sodium dodecyl sulfonate in 27.67g of deionized water, adding the sodium dodecyl sulfonate and 10g of 3- (methacryloyloxy) propyl trimethoxy silane into a reaction device, stirring uniformly, adding 0.16g of ammonium persulfate into the solution, and reacting for 8 hours at 70 ℃ to obtain the organosilicon modified starch A.
Then, the raw materials and the method for preparing the organosilicon modified starch adhesive are as follows: silicone modified starch a7.7G, surfactant B (polyether modified siloxane) 0.1G, water repellent C (wark silicone oil) 8.8G, modified mineral oil D0.4G, cross-linking agent E (hexamethoxymethyl melamine) 5.2G, catalyst F (p-toluene sulfonic acid) 0.1G, solvent G (deionized water 142.5G and n-propanol 35.2G). 8.8g of water repellent is added into 35.2g of normal propyl alcohol solvent, and is added into 142.5g of water together with the other raw materials, and finally the organosilicon modified starch adhesive is obtained after uniform stirring.
Finally, 200g of the organosilicon modified starch adhesive is uniformly sprayed on a single layer with the thickness of 0.6-0.8mm and the size of 12x12cm 2 And 20 layers of glass fiber cotton are sprayed and paved in sequence, and the glass fiber cotton is fixed by a glass plate, wherein the thickness of the glass fiber cotton is 25mm. And (3) placing the fixed glass fiber cotton into an oven, and performing thermosetting at 120 ℃ for 3 hours to obtain a glass fiber cotton product.
Comparative example 5
The raw materials, the dosage and the preparation method for preparing the organosilicon modified starch in the comparative example are as follows: firstly, 9.9g of corn starch is weighed and added into a reaction device, and then 30g of deionized water is added, so that the corn starch is uniformly dispersed in water; adding 9.9-g N-methylol acrylamide and 0.2g of catalyst p-toluenesulfonic acid, and then starting a stirrer to enable the mixed solution to react for 2 hours at 90 ℃; after the reaction is completed, the reaction device is cooled at room temperature to obtain P0; weighing and dissolving 1.6g of P0, 0.5g of NP-10 and 0.5g of sodium dodecyl sulfonate in 27.67g of deionized water, adding the sodium dodecyl sulfonate and 10g of 3- (methacryloyloxy) propyl trimethoxy silane into a reaction device, stirring uniformly, adding 0.16g of ammonium persulfate into the solution, and reacting for 8 hours at 70 ℃ to obtain the organosilicon modified starch A.
Then, the raw materials and the method for preparing the organosilicon modified starch adhesive are as follows: silicone modified starch a7.7G, surfactant B (polyether modified siloxane) 0.1G, water repellent C (tile silicone oil) 4G, modified mineral oil D0.4G, cross-linking agent E (hexamethoxymethyl melamine) 0.4G, catalyst F (p-toluene sulfonic acid) 0.1G, solvent G (deionized water 151.7G and n-propanol 35.2G). 8.8g of water repellent is added into 35.2g of normal propyl alcohol solvent, and is added into 151.7g of water together with the other raw materials, and finally the organosilicon modified starch adhesive is obtained after uniform stirring.
Finally, 200g of the organosilicon modified starch adhesive is uniformly sprayed on a single layer with the thickness of 0.6-0.8mm and the size of 12x12cm 2 And 20 layers of glass fiber cotton are sprayed and paved in sequence, and the glass fiber cotton is fixed by a glass plate, wherein the thickness of the glass fiber cotton is 25mm. And (3) placing the fixed glass fiber cotton into an oven, and performing thermosetting at 240 ℃ for 2 hours to obtain a glass fiber cotton product.
Comparative example 6
The raw materials, the dosage and the preparation method for preparing the organosilicon modified starch in the comparative example are as follows: firstly, 9.9g of corn starch is weighed and added into a reaction device, and then 30g of deionized water is added, so that the corn starch is uniformly dispersed in water; adding 9.9-g N-methylol acrylamide and 0.2g of catalyst p-toluenesulfonic acid, and then starting a stirrer to enable the mixed solution to react for 2 hours at 90 ℃; after the reaction is completed, the reaction device is cooled at room temperature to obtain P0; weighing and dissolving 6g of P0, 0.5g of NP-10 and 0.5g of sodium dodecyl sulfonate in 28.6g of deionized water, adding the sodium dodecyl sulfonate and 6g of 3- (methacryloyloxy) propyl trimethoxy silane into a reaction device, stirring uniformly, adding 0.16g of ammonium persulfate into the solution, and reacting for 8 hours at 70 ℃ to obtain the organosilicon modified starch A.
Then, the raw materials and the amounts of the organic silicon modified starch adhesive prepared in this comparative example are as follows: silicone modified starch a7.7G, surfactant B (polyether modified siloxane) 0.1G, water repellent C (wark silicone oil) 8.8G, modified mineral oil D0.4G, cross-linking agent E (hexamethoxymethyl melamine) 0.4G, catalyst F (p-toluene sulfonic acid) 0.1G, solvent G (deionized water 147.3G and n-propanol 35.2G). 8.8g of water repellent is added into 35.2g of normal propyl alcohol solvent, and is added into 147.3g of water together with the other raw materials, and finally the organosilicon modified starch adhesive is obtained after uniform stirring.
Finally, 200g of the organosilicon modified starch adhesive is uniformly sprayed on a single layer with the thickness of 0.6-0.8mm and the size of 12x12cm 2 And 20 layers of glass fiber cotton are sprayed and paved in sequence, and the glass fiber cotton is fixed by a glass plate, wherein the thickness of the glass fiber cotton is 25mm. And (3) placing the fixed glass fiber cotton into an oven, and performing thermosetting at 240 ℃ for 2 hours to obtain a glass fiber cotton product.
Comparative example 7
The raw materials, the dosage and the preparation method for preparing the organosilicon modified starch in the comparative example are as follows: firstly, 9.9g of corn starch is weighed and added into a reaction device, and then 30g of deionized water is added, so that the corn starch is uniformly dispersed in water; adding 9.9-g N-methylol acrylamide and 0.2g of catalyst p-toluenesulfonic acid, and then starting a stirrer to enable the mixed solution to react for 2 hours at 90 ℃; after the reaction is completed, the reaction device is cooled at room temperature to obtain P0; weighing and dissolving 6g of P0, 0.5g of NP-10 and 0.5g of sodium dodecyl sulfonate in 28.6g of deionized water, adding the sodium dodecyl sulfonate and 6g of 3- (methacryloyloxy) propyl trimethoxy silane into a reaction device, stirring uniformly, adding 0.16g of ammonium persulfate into the solution, and reacting for 8 hours at 70 ℃ to obtain the organosilicon modified starch A.
Then, the raw materials and the method for preparing the organosilicon modified starch adhesive are as follows: 5.3G of organosilicon modified starch A, 0.1G of surfactant B (polyether modified siloxane), 8.8G of water repellent C (tile silicone oil), 0.4G of modified mineral oil D, 0.4G of cross-linking agent E (hexamethoxymethyl melamine), 0.1G of catalyst F (p-toluenesulfonic acid), and solvent G (deionized water 154.1G and n-propanol 35.2G). 8.8g of water repellent is added into 35.2g of normal propyl alcohol solvent, and is added into 154.1g of water together with the other raw materials, and finally the organosilicon modified starch adhesive is obtained after uniform stirring.
Finally, 200g of the organosilicon modified starch adhesive is uniformly sprayed on a single layer with the thickness of 0.6-0.8mm and the size of 12x12cm 2 And 20 layers of glass fiber cotton are sprayed and paved in sequence, and the glass fiber cotton is fixed by a glass plate, wherein the thickness of the glass fiber cotton is 25mm. And (3) placing the fixed glass fiber cotton into an oven, and performing thermosetting at 240 ℃ for 2 hours to obtain a glass fiber cotton product.
Comparative example 8
The raw materials, the dosage and the preparation method for preparing the organosilicon modified starch in the comparative example are as follows: firstly, 9.9g of corn starch is weighed and added into a reaction device, and then 30g of deionized water is added, so that the corn starch is uniformly dispersed in water; adding 9.9-g N-methylol acrylamide and 0.2g of catalyst p-toluenesulfonic acid, and then starting a stirrer to enable the mixed solution to react for 2 hours at 90 ℃; after the reaction is completed, the reaction device is cooled at room temperature to obtain P0; weighing and dissolving 6g of P0, 0.5g of NP-10 and 0.5g of sodium dodecyl sulfonate in 28.6g of deionized water, adding the sodium dodecyl sulfonate and 6g of 3- (methacryloyloxy) propyl trimethoxy silane into a reaction device, stirring uniformly, adding 0.16g of ammonium persulfate into the solution, and reacting for 8 hours at 70 ℃ to obtain the organosilicon modified starch.
Then, the raw materials and the method for preparing the organosilicon modified starch adhesive are as follows: 5.3G of organosilicon modified starch A, 0.1G of surfactant B (polyether modified siloxane), 8.8G of water repellent C (tile silicone oil), 0.4G of modified mineral oil D, 0.4G of cross-linking agent E (hexamethoxymethyl melamine), 0.1G of catalyst F (p-toluenesulfonic acid), and solvent G (deionized water 154.1G and n-propanol 35.2G). 8.8g of water repellent is added into 35.2g of normal propyl alcohol solvent, and is added into 154.1g of water together with the other raw materials, and finally the organosilicon modified starch adhesive is obtained after uniform stirring.
Finally, 150g of the organosilicon modified starch adhesive is uniformly sprayed on a single layer with the thickness of 0.6-0.8mm and the size of 12x12cm 2 And 20 layers of glass fiber cotton are sprayed and paved in sequence, and the glass fiber cotton is fixed by a glass plate, wherein the thickness of the glass fiber cotton is 25mm. And (3) placing the fixed glass fiber cotton into an oven, and performing thermosetting at 240 ℃ for 2 hours to obtain a glass fiber cotton product.
Comparative example 9
The comparative example adopts common starch to prepare a starch adhesive, and the raw materials and the dosage are as follows: corn starch A5.3G, surfactant B (polyether modified siloxane) 0.1G, water repellent C (tile silicone oil) 8.8G, modified mineral oil D0.4G, cross-linking agent E (hexamethoxymethyl melamine) 0.4G, catalyst F (p-toluene sulfonic acid) 0.1G, solvent G (deionized water 154.1G and n-propanol 35.2G) were weighed. 8.8g of water repellent is added into 35.2g of normal propyl alcohol solvent, and is added into 154.1g of water together with the other raw materials, and finally the organosilicon modified starch adhesive is obtained after uniform stirring.
Finally, 150g of the organosilicon modified starch adhesive is uniformly sprayed on a single layer with the thickness of 0.6-0.8mm and the size of 12x12cm 2 And 20 layers of glass fiber cotton are sprayed and paved in sequence, and the glass fiber cotton is fixed by a glass plate, wherein the thickness of the glass fiber cotton is 25mm. And (3) placing the fixed glass fiber cotton into an oven, and performing thermosetting at 240 ℃ for 2 hours to obtain a glass fiber cotton product.
Comparative example 10
The comparative example adopts common starch to prepare a starch adhesive, and the raw materials and the dosage are as follows: corn starch A5.3G, surfactant B (polyether modified siloxane) 0.1G, water repellent C (tile silicone oil) 8.8G, modified mineral oil D5.2G, cross-linking agent E (hexamethoxymethyl melamine) 0.4G, catalyst F (p-toluene sulfonic acid) 0.1G, solvent G (deionized water 149.31G and n-propanol 35.2G) were weighed. 8.8g of water repellent is added into 35.2g of normal propyl alcohol solvent, and is added into 149.3g of water together with the other raw materials, and finally the organosilicon modified starch adhesive is obtained after uniform stirring.
Finally, 150g of the organosilicon modified starch adhesive is mixedUniformly spraying on a single layer with thickness of 0.6-0.8mm and size of 12x12cm 2 And 20 layers of glass fiber cotton are sprayed and paved in sequence, and the glass fiber cotton is fixed by a glass plate, wherein the thickness of the glass fiber cotton is 25mm. And (3) placing the fixed glass fiber cotton into an oven, and performing thermosetting at 240 ℃ for 2 hours to obtain a glass fiber cotton product.
The evaluation of the properties of the glass wool prepared in example 1 and comparative examples 1 to 10 was made with reference to the following method:
mass wash rate: gravimetric method as shown in fig. 4, glass wool was washed in a beaker with stirring for 30min, and then dried in an oven at 70 c, and the mass before and after washing was measured to test the mass washing rate.
Water repellency: and placing the glass fiber cotton on a glass plate, ensuring that the water flushing direction and the surface of the glass fiber cotton are 45 degrees, flushing for 1h, wiping off the water on the surface after flushing, weighing by a balance, and calculating to obtain the hydrophobicity.
The results of the performance test of the glass fiber cotton prepared in example 1 and comparative examples 1 to 10 are shown in Table 1:
TABLE 1 Performance test results of glass fiber wool
As can be seen from Table 1, the raw material formulation and weight ratio of the silicone modified corn starch of example 1 are as follows, corn starch A 1 N-methylol acryloyl A based on 100 weight parts 2 100 parts of organosilicon A 3 1262 parts of ammonium persulfate A 4 20.2 parts of surfactant A 5 12.6% parts; implementation of the embodimentsThe raw material formulation and weight percentage of the organosilicon modified corn starch adhesive in example 1 are as follows, organosilicon modified starch A3.85%, surfactant B0.05%, water repellent C4.4%, modified mineral oil D0.2%, cross-linking agent E0.2%, catalyst F0.05%, solvent G91.25%. The volume weight, the hydrophobicity and the mass washing rate of the organosilicon modified starch glass fiber cotton in example 1 were 139mg/cm respectively 3 98.5% and 3%, and the hydrophobicity and the quality washing rate of the paint reach good performance indexes.
Comparative example 1 the total amount of the silicone-modified starch binder sprayed on glass fiber cotton was adjusted to 0.75 times that of example 1, compared to example 1, and the volume weight, the water repellency and the mass washing rate of the silicone-modified starch glass fiber cotton were 112mg/cm, respectively 3 96% and 5%, especially hydrophobic and quality wash performance, are reduced due to the reduced total amount of silicone modified starch binder, resulting in reduced hydrophobicity and thus reduced hydrophobic and quality wash performance.
Compared with the example 1, the weight part of the surfactant B in the raw material formula of the organosilicon modified corn starch adhesive is increased from 0.05% to 0.5%, and the volume weight, the hydrophobic rate and the mass washing rate of the organosilicon modified starch glass fiber cotton are respectively 98mg/cm 3 99.1% and 3.5%, the organosilicon modified corn starch and the water repellent can be well dispersed in the solvent due to the increase of the surfactant B, so that the water repellency rate of the organosilicon modified starch glass fiber cotton is increased.
Compared with the example 1, the weight part of the cross-linking agent E in the raw material formula of the organosilicon modified corn starch adhesive is increased from 0.2 percent to 2.6 percent, and the volume weight, the hydrophobic rate and the mass washing rate of the organosilicon modified starch glass fiber cotton are respectively 95mg/cm 3 The hydrophobicity and the quality washing rate of 98.2 percent and 4.5 percent reach good performance indexes, but the hydrophobicity and the quality washing performance of the cross-linking agent E are reduced to a certain extent due to the certain hydrophilicity of the cross-linking agent E.
Comparative example 4 Cross-linking in the raw Material formulation of Silicone-modified corn starch adhesive compared to example 1The weight part of the linking agent E is increased from 0.2 percent to 2.6 percent, the curing temperature and the curing time are respectively adjusted to 120 ℃ and 3 hours, and the volume weight, the hydrophobic rate and the mass washing rate of the organosilicon modified starch glass fiber cotton are respectively 101mg/cm 3 97.3% and 4%. Compared with the curing temperature and the curing time of the example 1, which are 240 ℃ and 2 hours, the curing temperature is greatly reduced, the mass production industrialization is facilitated, and the hydrophobicity is only reduced to 97.3%.
Compared with example 1, the weight part of the water repellent C in the raw material formula of the organosilicon modified corn starch adhesive is reduced from 4.4% to 2%, and the volume weight, the water repellent rate and the mass washing rate of the organosilicon modified starch glass fiber cotton are 55mg/cm < 3 >, 85% and 13.5%, respectively. After the hydrophobicity is reduced, the hydrophobicity of the organosilicon modified starch adhesive is reduced, and the hydrophobicity and the quality washing performance of the organosilicon modified starch adhesive are greatly reduced.
Compared with example 1, the raw material formulation and weight ratio of the organosilicon modified corn starch of comparative example 6 are as follows, corn starch A 1 N-methylol acryloyl A based on 100 weight parts 2 100 parts of organosilicon A 3 202 parts of ammonium persulfate A 4 5.4 parts of surfactant A 5 33.6% of the organic silicon modified starch glass fiber cotton with the volume weight, the hydrophobicity and the mass washing rate of 78mg/cm respectively 3 92% and 6%. Organosilicon A in raw material formula of organosilicon modified corn starch 3 The hydrophobicity of the organosilicon modified starch adhesive is reduced, so that the hydrophobicity and the quality washing performance are reduced.
Compared with example 1, the raw material formulation and weight ratio of the organosilicon modified corn starch of comparative example 7 are as follows, corn starch A 1 N-methylol acryloyl A based on 100 weight parts 2 100 parts of organosilicon A 3 202 parts of ammonium persulfate A 4 5.4 parts of surfactant A 5 33.6 parts; in addition, the specific gravity of the organosilicon modified starch in the organosilicon modified corn starch adhesive formula is reduced from 3.85% to 2.65%; the volume weight, the hydrophobicity and the mass washing rate of the organosilicon modified starch glass fiber cotton are respectively 47mg/cm 3 88% and 7%. From the following componentsOrganosilicon A in the raw material formulation of organosilicon modified corn starch 3 The weight ratio of the organosilicon modified corn starch in the organosilicon modified corn starch adhesive is reduced, so that the hydrophobicity of the organosilicon modified corn starch adhesive is greatly reduced, and the hydrophobicity and the quality washing performance of the organosilicon modified corn starch adhesive are reduced to a certain extent.
Compared with example 1, the raw material formulation and weight ratio of the organosilicon modified corn starch of comparative example 8 are as follows, corn starch A 1 N-methylol acryloyl A based on 100 weight parts 2 100 parts of organosilicon A 3 202 parts of ammonium persulfate A 4 5.4 parts of surfactant A 5 33.6 parts; in addition, the specific gravity of the organosilicon modified starch in the organosilicon modified corn starch adhesive formula is reduced to 2.65 percent by 3.85 percent, and the total weight of the organosilicon modified starch adhesive is regulated to be 0.75 times. The volume weight, the hydrophobicity and the mass washing rate of the organosilicon modified starch glass fiber cotton are respectively 89mg/cm 3 87%, and 10.3%. Because the organosilicon A in the raw material formula of the organosilicon modified corn starch 3 The weight ratio of the organic silicon modified corn starch in the organic silicon modified corn starch adhesive is reduced, and the total amount of the organic silicon modified corn starch adhesive is reduced, so that the hydrophobicity of the organic silicon modified corn starch adhesive and the glass fiber cotton is greatly reduced, and the hydrophobicity and the quality washing performance of the organic silicon modified corn starch adhesive are greatly reduced.
Compared with the example 1, the corn starch in the formula of the comparative example 9 is unmodified, the proportion of the corn starch in the formula of the corn starch adhesive is 2.65 percent, the total weight of the corn starch adhesive is 0.75 times that of the example 1, and the volume weight, the hydrophobic rate and the mass washing rate of the organosilicon modified starch glass fiber cotton are 86mg/cm respectively because the corn starch is not modified 3 The hydrophobic property and the quality washing property of the water-repellent paint are greatly reduced by 86 percent and 12 percent.
In comparison with example 1, the formulation of comparative example 10 was unmodified corn starch, the corn starch proportion in the formulation of the corn starch binder was 2.65%, the proportion of the crosslinking agent E was increased to 2.6%, and the total weight of the corn starch binder was 0.7 of example 15 times, the volume weight, the hydrophobicity and the mass washing rate of the organosilicon modified starch glass fiber cotton are respectively 54mg/cm 3 82% and 20%. The hydrophobic properties and the quality washing properties were reduced to a greater extent than in example 1 and comparative example 9.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (9)
1. The organic silicon modified starch glass fiber cotton is characterized in that the preparation method comprises the following steps: uniformly spraying an organosilicon modified starch adhesive on the surface of glass fiber, and performing high-temperature thermal curing to obtain organosilicon modified starch glass fiber cotton; the organosilicon modified starch adhesive is prepared by uniformly stirring organosilicon modified starch A, a surfactant B, a water repellent C, modified mineral oil D, a cross-linking agent E, a catalyst F and a solvent G according to a certain proportion; the organosilicon modified starch A endows starch with excellent hydrophobicity, is a polymer of random or block organosilicon modified starch synthesized by an organosilicon containing unsaturated double bonds and starch containing unsaturated double bonds in a free radical polymerization mode, and simultaneously reacts with hydroxyl groups on the surface of glass fibers by using siloxane functional groups of the polymer as a coupling agent, so that the starch and the glass fibers are chemically connected, and the organosilicon modified starch glass fiber cotton has excellent hydrophobicity, quality washing resistance and mechanical properties.
2. The organic silicon modified starch glass fiber cotton according to claim 1, wherein the specific preparation method of the organic silicon modified starch A is as follows: by starch A 1 Compound A containing unsaturated double bond modified and grafted by medium hydroxyl functional group 2 Then with organic silicon A containing unsaturated double bond 3 Free radical polymerization is carried out, and its typical molecular structural formula is as follows:
the number average molecular weight of the organosilicon modified starch is 23000-1000000, wherein x is the polymerization degree of glucose in the starch, y is the polymerization degree of unsaturated double bond modified starch, and z is the polymerization degree of unsaturated double bond containing organosilicon;
starch A 1 Is one or more of corn starch, mung bean starch, wheat starch, sweet potato starch and tapioca starch, and has hydroxyl functional group in molecular structure and unsaturated double bond-containing compound A 2 Grafting reaction, and simultaneously, participating in crosslinking curing reaction with a crosslinking agent in the organosilicon modified starch adhesive;
compound A containing unsaturated double bond 2 Wherein R is 1 Is H or CH 3 ，A 2 Is one or more of N-methylolacrylamide, N-methylolmethacrylamide, acryloyl chloride, methacryloyl chloride and maleic anhydride, and is structurally characterized in that hydroxyl in the molecular structure is mixed with starch A under the acid catalysis condition 1 Etherification reaction of hydroxyl groups in the molecular structure;
organosilicon A containing unsaturated double bonds 3 Wherein R is 2 Is H or CH 3 ，R 3 Is an alkane chain with 1-10 carbon atoms, A 3 Is a mixture of one or more compounds containing unsaturated double bonds;
finally, in the free radical polymerization process of the organosilicon modified starch, an initiator A is added 4 And surfactant A 5 The initiator A 4 Ammonium persulfate as surfactant A 5 Is one or two of sodium dodecyl sulfonate and NP-10.
3. The organic silicon modified starch glass fiber cotton according to claim 2, wherein the organic silicon modified starch A comprises the following raw materials in parts by weight: starch A 1 100 parts of unsaturated double bond-containing compound A 2 10-125 parts of organic silicon A containing unsaturated double bonds 3 50 to 1500 parts of initiator A 4 1-30 parts of surfactant A 5 10-80 parts.
4. The silicone-modified starch glass fiber cotton of claim 3 wherein the silicone-modified starch a is prepared by a two-step reaction: first, starch A 1 And a compound A containing unsaturated double bonds 2 The intermediate product is synthesized by reacting an acid catalyst in a solution at 60-120 ℃ for 1-10 hours, and is called P0; second P0 and organosilicon A containing unsaturated double bonds 3 Proportionally adding initiator A 4 And surfactant A 5 The organosilicon modified starch A is prepared by a free radical polymerization mode, the solution polymerization temperature is 60-95 ℃, and the reaction time is 2-10h.
5. The organic silicon modified starch glass fiber cotton according to claim 1, wherein the surfactant B is one or more of siloxane, polyether modified siloxane and fluorocarbon siloxane, the average molecular weight of the organic silicon modified starch glass fiber cotton is 3000-200000, and the mass percentage of a siloxane chain segment and a polyether chain segment is 25-100%; the hydrophobic agent C is silicone oil, the average molecular weight of the hydrophobic agent C is 5000-250000, and the viscosity of the hydrophobic agent C is 100-1000 CPS; the modified mineral oil D is mineral oil LD-702, and the viscosity is 800 CPS-60000 CPS; the cross-linking agent E is one or more of polyfunctional isocyanate compounds, glycoluril resins, phenolic resins and amino resins; the catalyst F is one or more of p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, p-dodecylbenzenesulfonic acid and perfluorooctane sulfonic acid; the solvent G is one or more of alcohol organic solvents and water.
6. The silicone modified starch glass fiber cotton of claim 1, wherein the silicone modified starch binder comprises, in weight percent: 1 to 20 percent of organosilicon modified starch A, 0.001 to 1 percent of surfactant B, 0.5 to 20 percent of water repellent C, 0.1 to 1 percent of modified mineral oil D, 0.08 to 10 percent of cross-linking agent E, 0.01 to 0.2 percent of catalyst F and 80 to 95 percent of solvent G.
7. The silicone-modified starch glass fiber cotton of claim 6, wherein the silicone-modified starch binder is prepared by the following steps: and uniformly mixing the organosilicon modified starch A, the surfactant B, the water repellent C, the modified mineral oil D, the cross-linking agent E, the catalyst F and the solvent G, stirring for 10-20min, and then standing for 1h to prepare the organosilicon modified starch adhesive.
8. The organic silicon modified starch glass fiber cotton according to any one of claims 1 to 7, wherein the specific preparation method is as follows: spraying the organosilicon modified starch adhesive to the surface of the single-layer glass fiber cotton in mist droplets to obtain the organosilicon modified starch adhesive single-layer glass fiber cotton; and preparing blocky glass fiber cotton by paving the organosilicon modified starch adhesive single-layer glass fiber cotton layer by layer; finally, shaping by a clamp, and curing at a high temperature in an oven at 120-260 ℃ for 30-200min to prepare the organosilicon modified starch glass fiber cotton.
9. The organic silicon modified starch glass fiber cotton according to claim 8, wherein the organic silicon modified starch glass fiber cotton has a hydrophobic rate of more than 98% and a mass washing rate of less than 5% and is applied to heat preservation, heat insulation and sound insulation materials in the fields of construction, automobiles, household appliances, electronics and chemical industry.
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