CN115232335A - Novel polymer gel material for soft rubber toy and preparation process thereof - Google Patents
Novel polymer gel material for soft rubber toy and preparation process thereof Download PDFInfo
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- CN115232335A CN115232335A CN202211048317.3A CN202211048317A CN115232335A CN 115232335 A CN115232335 A CN 115232335A CN 202211048317 A CN202211048317 A CN 202211048317A CN 115232335 A CN115232335 A CN 115232335A
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- polyvinyl alcohol
- water
- gel material
- potassium
- ion source
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- 239000000463 material Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 229920000642 polymer Polymers 0.000 title description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 92
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 92
- 238000004132 cross linking Methods 0.000 claims abstract description 57
- 239000001257 hydrogen Substances 0.000 claims abstract description 44
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 44
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 32
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 42
- 239000003292 glue Substances 0.000 claims description 41
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 36
- 239000000084 colloidal system Substances 0.000 claims description 22
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 19
- VXJIMUZIBHBWBV-UHFFFAOYSA-M lithium;chloride;hydrate Chemical compound [Li+].O.[Cl-] VXJIMUZIBHBWBV-UHFFFAOYSA-M 0.000 claims description 19
- 231100000252 nontoxic Toxicity 0.000 claims description 19
- 230000003000 nontoxic effect Effects 0.000 claims description 19
- 239000001103 potassium chloride Substances 0.000 claims description 18
- 235000011164 potassium chloride Nutrition 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 229910021645 metal ion Inorganic materials 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 239000003995 emulsifying agent Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000000022 bacteriostatic agent Substances 0.000 claims description 8
- 229910021538 borax Inorganic materials 0.000 claims description 8
- 239000003086 colorant Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000004328 sodium tetraborate Substances 0.000 claims description 8
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- -1 borax) Chemical compound 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 7
- 238000004806 packaging method and process Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- WOKDXPHSIQRTJF-UHFFFAOYSA-N 3-[3-[3-[3-[3-[3-[3-[3-[3-(2,3-dihydroxypropoxy)-2-hydroxypropoxy]-2-hydroxypropoxy]-2-hydroxypropoxy]-2-hydroxypropoxy]-2-hydroxypropoxy]-2-hydroxypropoxy]-2-hydroxypropoxy]-2-hydroxypropoxy]propane-1,2-diol Chemical compound OCC(O)COCC(O)COCC(O)COCC(O)COCC(O)COCC(O)COCC(O)COCC(O)COCC(O)COCC(O)CO WOKDXPHSIQRTJF-UHFFFAOYSA-N 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 5
- CHHHXKFHOYLYRE-UHFFFAOYSA-M 2,4-Hexadienoic acid, potassium salt (1:1), (2E,4E)- Chemical compound [K+].CC=CC=CC([O-])=O CHHHXKFHOYLYRE-UHFFFAOYSA-M 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000002372 labelling Methods 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 239000004302 potassium sorbate Substances 0.000 claims description 4
- 235000010241 potassium sorbate Nutrition 0.000 claims description 4
- 229940069338 potassium sorbate Drugs 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002537 cosmetic Substances 0.000 claims description 3
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 238000010009 beating Methods 0.000 claims description 2
- 239000000796 flavoring agent Substances 0.000 claims description 2
- 235000013355 food flavoring agent Nutrition 0.000 claims description 2
- 239000008098 formaldehyde solution Substances 0.000 claims description 2
- 238000005461 lubrication Methods 0.000 claims description 2
- 238000013508 migration Methods 0.000 claims description 2
- 230000005012 migration Effects 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- 235000013599 spices Nutrition 0.000 claims description 2
- 230000003068 static effect Effects 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims 2
- 239000002184 metal Substances 0.000 claims 2
- 239000002304 perfume Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 10
- 230000003749 cleanliness Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000004134 energy conservation Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000005303 weighing Methods 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 5
- XMGQYMWWDOXHJM-JTQLQIEISA-N (+)-α-limonene Chemical compound CC(=C)[C@@H]1CCC(C)=CC1 XMGQYMWWDOXHJM-JTQLQIEISA-N 0.000 description 4
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229940079593 drug Drugs 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 244000248349 Citrus limon Species 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000013373 food additive Nutrition 0.000 description 2
- 239000002778 food additive Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011344 liquid material Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- UJMBCXLDXJUMFB-GLCFPVLVSA-K tartrazine Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=NN(C=2C=CC(=CC=2)S([O-])(=O)=O)C(=O)C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 UJMBCXLDXJUMFB-GLCFPVLVSA-K 0.000 description 2
- 235000012756 tartrazine Nutrition 0.000 description 2
- 239000004149 tartrazine Substances 0.000 description 2
- UJMBCXLDXJUMFB-UHFFFAOYSA-K trisodium;5-oxo-1-(4-sulfonatophenyl)-4-[(4-sulfonatophenyl)diazenyl]-4h-pyrazole-3-carboxylate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=NN(C=2C=CC(=CC=2)S([O-])(=O)=O)C(=O)C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 UJMBCXLDXJUMFB-UHFFFAOYSA-K 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- AXISYYRBXTVTFY-UHFFFAOYSA-N Isopropyl tetradecanoate Chemical compound CCCCCCCCCCCCCC(=O)OC(C)C AXISYYRBXTVTFY-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
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- 239000004033 plastic Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63H—TOYS, e.g. TOPS, DOLLS, HOOPS OR BUILDING BLOCKS
- A63H9/00—Special methods or compositions for the manufacture of dolls, toy animals, toy figures, or parts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/247—Heating methods
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention provides a gel material formed by carrying out hydrogen bond thermal crosslinking on polyvinyl alcohol in a water phase by lithium ion auxiliary potassium ions and a hydrogen bond thermal crosslinking preparation process thereof, and a scheme for preparing a boron-free soft rubber toy by using the hydrogen bond thermal crosslinking gel material is formulated, wherein the gel material and the preparation process are characterized in that gel main body components comprise the following components in percentage by mass: 60% -75.5% of deionized water, 1750 +/-50% -15% of polyvinyl alcohol, 7.5% -10% of water-soluble lithium ion source and 5% -7.5% of water-soluble potassium ion source. The hydrogen bond thermal crosslinking gel material prepared by the invention has the remarkable advantages of no toxic and harmful substances, uniform components, less detention, simple preparation method and process, high mechanical automation degree in the preparation process, high cleanliness, low production cost, energy conservation, high efficiency, environmental friendliness, suitability for industrial production and the like.
Description
Technical Field
The invention relates to the technical field of preparation and application of high polymer materials, in particular to design and preparation of a non-toxic low-residue viscoelastic high polymer material and application of the non-toxic low-residue viscoelastic high polymer material in the field of safety toys.
Background
The soft rubber toy is a very popular toy type in recent years, and accounts for about 10 percent of the market of children toys. At present, the toy is generally prepared by adding wood glue or daily glue into a medium-low concentration sodium tetraborate (borax) aqueous solution for crosslinking to form a gel material which takes boron atoms as a center and boric acid ester as a framework as a main body and manually mixing other materials. The borate gel material has a very high occupancy in the market of soft rubber toys, target groups of the toys are students in middle and primary schools and children in low ages, and part of the target groups also enter the visual field of office workers and parents.
However, toy materials with such high market share have a great safety hazard. The storefronts selling the soft mud toys are examined on line and off line, and the soft rubber toys which are sold in the market and take the boric acid ester gel material as the main body are found to have the following defects:
(1) The existing soft rubber toys in the market use a large amount of borax and woodwork glue, and are added with glycerol as a water retention agent. Wherein, borax has biotoxicity, accumulated toxicity and carcinogenicity, formaldehyde is easy to separate out from part of raw material glue, and water-retaining agents such as glycerol and the like which can form boric acid ester can enhance the retention of harmful substances on hands, thereby bringing hidden danger to the safety of children toys. And students and children are also liable to take harmful substances in this case.
(2) As the existing market just starts to rise, the definition of the toy is not sufficient and the components of the upstream raw materials are not fixed by the merchant, so that the components of the gel material related to the existing soft rubber toy in the market cannot be fixed in a standard mode and have no component repeatability.
(3) The mixing preparation process of the existing soft rubber toy in the market is that a plurality of mixtures are mixed with each other, so that defective products with uneven substance concentration caused by the fact that raw materials cannot be compatible and local mixing is insufficient due to poor stability and different viscosity of the raw materials are easy to occur.
(4) The mixing preparation process of the existing soft rubber toy in the market is mostly operated manually, and the sanitary requirements of controlling the cleanliness degree of the final toy product, the total number of bacterial colonies and the like are difficult to achieve.
(5) The gel material taking borate as the framework is also harmful to the environment, and if the soft rubber toy taking the material as the main body is abandoned, the gel material is not friendly to the environment.
The technologies required by the defects are the main blank of the prior background technology in the market of the existing soft rubber toy and the main material thereof, so that the standardized non-toxic soft rubber toy product is difficult to produce so far.
In view of the above, there is a need for an environment-friendly gel material that completely eliminates borate backbone and has a high-safety fixed formulation, and that can match a corresponding automated and clean high-efficiency preparation process.
Disclosure of Invention
Aiming at the blank of the existing background technology of the soft rubber toy and the main material market thereof, the invention aims to provide a hydrophilic gel material which takes nontoxic light metal ions as the center and takes hydrogen bond crosslinking as a framework, and provides a hydrogen bond thermal crosslinking preparation process with fixed formula, mechanical automation of production and clean production process.
In order to achieve the aim and the aim that the material is applied to other production and research directions, the invention provides a gel material formed by carrying out hydrogen bond thermal crosslinking on polyvinyl alcohol in an aqueous phase by lithium ion-assisted potassium ions, a hydrogen bond thermal crosslinking preparation process thereof, and a scheme for preparing a boron-free soft rubber toy by using the hydrogen bond thermal crosslinking gel material. The gel material and the preparation process are characterized in that:
the gel comprises the following main components in percentage by mass:
60 to 75.5 percent of deionized water
1750 +/-50% -15% of polyvinyl alcohol
7.5 to 10 percent of water-soluble lithium ion source (lithium chloride monohydrate, and other lithium-containing compounds converted according to the molar mass ratio of the lithium ions)
5 to 7.5 percent of water-soluble potassium ion source (potassium chloride, and other potassium-containing compounds calculated according to the molar mass ratio of potassium ions)
Preferably, the gel main body component comprises the following components in percentage by mass:
deionized water 75.5%
1750 +/-50.5% of polyvinyl alcohol
7.5% of water-soluble lithium ion source (lithium chloride monohydrate, other lithium-containing compounds calculated according to the molar mass ratio of lithium ions)
Water-soluble potassium ion source (potassium chloride, other potassium-containing compounds calculated by potassium ion molar mass ratio) 7.5%
The preparation process of the gel by hydrogen bonding and thermal crosslinking comprises the following steps:
(1) At normal pressure and 70-95 deg.c, deionized water is used to dissolve PVA to form PVA colloid, rather than formaldehyde, its water solution or hydrochloric acid as solvent.
(2) The polyvinyl alcohol colloid is preliminarily crosslinked by using a water-soluble lithium ion source (lithium chloride monohydrate) at the temperature of between 80 and 90 ℃ under normal pressure to form a polyvinyl alcohol colloid solution.
(3) The gel material is obtained by completely crosslinking polyvinyl alcohol glue solution by using a water-soluble potassium ion source (potassium chloride) at the temperature of between 60 and 80 ℃ under normal pressure.
(4) If the polyvinyl alcohol glue solution does not form gel, reduced pressure distillation at 70-90 ℃ can be adopted to promote the generation of the gel material.
Preferably, the preparation process of the gel material by hydrogen bonding and thermal crosslinking comprises the following steps:
(1) The polyvinyl alcohol is dissolved in deionized water at 92 deg.C and normal pressure to form polyvinyl alcohol colloid, and formaldehyde and its aqueous solution or hydrochloric acid are not used as solvent.
(2) The polyvinyl alcohol colloid was preliminarily crosslinked at 85 ℃ under normal pressure using a water-soluble lithium ion source (lithium chloride monohydrate) to form a polyvinyl alcohol colloidal solution.
(3) The gel material was obtained by completely crosslinking the polyvinyl alcohol gel solution at 70 ℃ under normal pressure using a water-soluble potassium ion source (potassium chloride).
(4) If the polyvinyl alcohol glue solution does not form gel, a method of reduced pressure distillation at 87 ℃ can be adopted to promote the generation of the gel material.
The scheme for preparing the soft rubber toy by taking the hydrogen bond thermal crosslinking gel material as a main body comprises the following steps:
(1) The required deionized water, polyvinyl alcohol 1750 +/-50, water-soluble lithium ion source (lithium chloride monohydrate), water-soluble potassium ion source (potassium chloride), water-retaining agent, bacteriostatic agent, emulsifier, aromatizing agent and colorant are calculated and obtained in advance according to the mass percentage of the gel main components.
(2) The polyvinyl alcohol is dissolved in deionized water at 92 deg.C and normal pressure to form polyvinyl alcohol colloid, and formaldehyde and its aqueous solution or hydrochloric acid are not used as solvent.
(3) The polyvinyl alcohol colloid was preliminarily crosslinked at 85 ℃ under normal pressure using a water-soluble lithium ion source (lithium chloride monohydrate) to form a polyvinyl alcohol colloidal solution.
(4) Decaglycerol with the mass percent of 1% is added into the preliminarily crosslinked polyvinyl alcohol glue solution to serve as a water retention agent.
(5) And adding 1% by mass of potassium sorbate as a bacteriostatic agent into the preliminarily crosslinked polyvinyl alcohol glue solution.
(6) And adding 1 percent of emulsifier for cosmetics in percentage by mass into the preliminarily crosslinked polyvinyl alcohol glue solution to serve as an emulsifier.
(7) Adding 0.5 percent of natural spice extract or edible essence by mass percent into the preliminarily crosslinked polyvinyl alcohol glue solution to be used as a flavoring agent.
(8) Adding 0.2 percent of water-soluble edible pigment by mass percentage into the preliminarily crosslinked polyvinyl alcohol glue solution to be used as a coloring agent.
(9) The gel material is obtained by completely crosslinking polyvinyl alcohol glue solution by using a water-soluble potassium ion source (potassium chloride) at normal pressure and 70 ℃, and if the polyvinyl alcohol glue solution does not form gel, the gel material can be promoted to generate by adopting a reduced pressure distillation method at 87 ℃, so that the soft rubber toy taking the thermal crosslinking gel material as a main body is formed.
(10) Cooling the soft rubber toy with the thermal crosslinking gel material as the main body to normal temperature, carrying out vacuum defoaming, adding a proper amount of other solid toys or decorative particles which are compatible and compliant with the components of the soft rubber toy as fillers, and subpackaging the obtained mixture into a container for sealing, labeling and packaging.
Preferably, the gel material formed by hydrogen bond thermal crosslinking of polyvinyl alcohol in an aqueous phase by lithium ion-assisted potassium ions is formed by taking nontoxic light metal ions such as lithium ions and potassium ions as a center and taking hydrogen bond crosslinking with polyvinyl alcohol as a skeleton, but not taking ester bond crosslinking with polyacid as a center.
Preferably, each step in the gel material and hydrogen bond thermal crosslinking preparation process can be compatible with at least one or more of water-retaining agent, bacteriostatic agent, emulsifier, aromatizing agent and colorant to form the soft gum toy, and an appropriate amount of other solid toys or decorative particles which are compatible and compatible with the soft gum toy components can be added into the soft gum toy as filler.
Preferably, the gel material, the hydrogen bond thermal crosslinking preparation process and the scheme for preparing the soft rubber toy by taking the hydrogen bond thermal crosslinking gel material as the main body do not contain or relate to sodium tetraborate (borax), formaldehyde and aqueous solution thereof and other ingredients listed in the current national standard GB6675: migration elements in toy safety.
Preferably, the hydrogen bond thermal crosslinking preparation process of the gel material can be completely carried out in a reaction kettle through mechanical stirring, then the gel material is discharged into a sterilized clean container through a liquid valve, and operations such as vacuum defoaming, storage and transportation are carried out in batches, and the raw materials can be sterilized at high temperature in the preparation process, so that the mechanical automation, cleaning and aseptic operation can be easily realized.
Preferably, the water-retaining agent decaglycerol used in the scheme of preparing the soft rubber toy by taking the hydrogen bond thermal crosslinking gel material as the main body is polyether instead of polyol, the substance is not easy to crosslink with boric acid to form boric acid ester, has strong hydrophilicity, and can reduce the residual degree of toy components while keeping water lubrication.
Preferably, the soft rubber toy prepared by the scheme of taking the hydrogen bond thermal crosslinking gel material as a main body has good mechanical property, and can withstand high-strength mechanical operations such as pulling and beating when the toy is abused reasonably; because the gel material takes nontoxic light metal ions such as lithium ions and potassium ions as the center and takes hydrogen bond crosslinking with polyvinyl alcohol as a framework, the gel material can self-repair intramolecular damage caused by hydrogen bond fracture in a water retention static state for several hours to several days after being subjected to mechanical operation.
Preferably, the main material and other auxiliary aids and substances involved in the scheme of preparing the soft rubber toy by taking the hydrogen bond thermal crosslinking gel material as the main body have no environmental hazard.
The gel material which is prepared by the invention and takes nontoxic light metal ions such as lithium ions and potassium ions as the center and takes hydrogen bond thermal crosslinking with polyvinyl alcohol as the framework has the obvious advantages of no toxic and harmful substances, uniform components, less detention, simple preparation method and process, high mechanical automation degree of the preparation process, high cleanliness, low production cost, energy conservation, high efficiency, environmental friendliness, suitability for industrial production and the like.
Drawings
FIG. 1 is a schematic diagram of a hydrogen-bonding thermal-crosslinking technique and a structural diagram of a gel material formed by performing hydrogen-bonding thermal-crosslinking on polyvinyl alcohol in an aqueous phase with lithium ion-assisted potassium ions.
FIG. 2 is a schematic view of the apparatus of examples 1 and 2 of the present invention, wherein the heat source, the holding means, and the stirring means are omitted, the reactor is a three-necked round-bottomed flask, and the temperature of the reaction to be monitored is indicated by a thermometer. The drawings are mainly for the purpose of illustration and are therefore not meant to be brand and parameter.
FIG. 3 is an enlarged view of a partial structure of the surface of the gel material prepared in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims.
The embodiment of the invention provides a preparation method of a gel material formed by performing hydrogen bond heat crosslinking on polyvinyl alcohol in an aqueous phase by using lithium ion-assisted potassium ions, and a preparation method of a soft rubber toy taking the hydrogen bond heat crosslinking gel material as a main body.
The following are typical but non-limiting examples of the invention:
example 1:
the implementation provides a preparation method of a gel material formed by carrying out hydrogen bonding thermal crosslinking on polyvinyl alcohol in an aqueous phase by using lithium ion to assist potassium ions, and the method comprises the following steps:
(1) Weighing 1750 +/-50 g of polyvinyl alcohol (50.0002 g) particles at 20 ℃, putting the particles into a clean four-neck single-layer cylindrical round bottom glass reaction kettle with a mechanical stirrer (sealed by a polytetrafluoroethylene stirring plug with a 24/29 standard port), a reflux condenser pipe with a 24/29 standard port and 500mm (connected with a piston 90-degree suction joint with the 24/29 standard port), a feeding port (connected with a 250ml constant-pressure dropping funnel with the 24/29 standard port to add liquid materials and connected with a phi 75mm triangular feeding funnel with the 24/29 standard port to add solid materials) and a phi 150mm flange with a 200mm thermometer sleeve with the 24/29 standard port and an outer diameter of 500ml with the 24/29 standard port, and monitoring the internal reaction temperature by a thermocouple for standby.
(2) Weighing 400.0017g of deionized water at 20 ℃, adding the deionized water into a reaction kettle, heating to 92 ℃, stirring at a constant temperature of 300rpm for 2 hours by a mechanical stirrer until polyvinyl alcohol particles are dissolved to form polyvinyl alcohol colloid, continuously stirring after the polyvinyl alcohol particles are completely dissolved, and keeping the temperature to 85 ℃ for later use.
(3) Weighing 40.0015g of lithium chloride monohydrate solid particles at 20 ℃, adding the lithium chloride monohydrate solid particles into a reaction kettle, stirring at a constant temperature of 85 ℃ until the lithium chloride monohydrate solid is completely dissolved to form a polyvinyl alcohol glue solution, continuously stirring for 3min, and keeping the temperature to 70 ℃ for later use. After the polyvinyl alcohol glue solution is cooled, a layer of partially cross-linked glue film can be formed on the surface.
(4) Weighing 40.0012g of potassium chloride solid powder at 20 ℃, stirring at constant temperature of 500rpm of a mechanical stirrer at 70 ℃, adding into a reaction kettle, and forming the hydrogen bond thermal crosslinking gel material after the potassium chloride solid powder is completely dissolved and crosslinked.
Example 2:
the implementation provides a preparation method of a soft rubber toy taking the hydrogen bond thermal crosslinking gel material as a main body, and the method comprises the following steps:
(1) Weighing 1750 +/-50 g of polyvinyl alcohol at 20 ℃, placing the particles into a clean four-neck single-layer cylindrical round bottom glass reaction kettle with a mechanical stirrer (sealed by a 24/29 standard-opening polytetrafluoroethylene stirring plug), a 24/29 standard-opening 500mm reflux condenser tube (connected with a 24/29 standard-opening piston 90-degree suction joint at the upper part), a feed opening (connected with a 250ml constant-pressure dropping funnel at the 24/29 standard opening to add liquid materials and connected with a 75mm triangular feed funnel at the 24/29 standard opening to add solid materials) and a 24/29 standard-opening 200mm thermometer sleeve, wherein the outer diameter of a flange is 150mm, the outer diameter of the flange is 500ml at the 24/29 standard opening, and the four-neck single-layer cylindrical round bottom glass reaction kettle is used for standby and the internal reaction temperature is monitored by a thermocouple.
(2) Weighing 400.0004g of deionized water at 20 ℃ and adding the deionized water into a reaction kettle, heating the deionized water to 92 ℃, stirring the deionized water at a constant temperature for 2 hours at 300rpm of a mechanical stirrer until polyvinyl alcohol particles are dissolved to form polyvinyl alcohol colloid, continuously stirring the polyvinyl alcohol colloid after the polyvinyl alcohol particles are completely dissolved, and keeping the temperature at 85 ℃ for later use.
(3) Weighing 40.0033g of lithium chloride monohydrate solid particles at 20 ℃ and adding the particles into a reaction kettle, stirring at constant temperature of 85 ℃ until the lithium chloride monohydrate solid is completely dissolved to form a polyvinyl alcohol glue solution, continuing stirring for 3min, and keeping the temperature to 70 ℃ for later use. After the glue solution is cooled, a layer of partially cross-linked glue film can be formed on the surface.
(4) Weighing 5.3013g of decaglycerol, 5.3001g of potassium sorbate, 5.3028g of span-80 (also called span-80, namely emulsifier S-80), 2.6504g of D-limonene (source: orange peel extraction) and 1.0601g of hydrazine yellow (also called lemon yellow, namely food additive acid yellow 23) at the temperature of 20 ℃, adding into a reaction kettle, stirring at the constant temperature of 400rpm of a mechanical stirrer for 5min to completely dissolve all additives and uniformly disperse the additives into polyvinyl alcohol glue solution, continuing to stir for 3min, and keeping the temperature to 70 ℃ for later use. After the glue solution is cooled, a layer of partially crosslinked glue film can be formed on the surface.
(5) Weighing 40.0010g of potassium chloride solid powder at 20 ℃, stirring at constant temperature of 70 ℃ and 500rpm of a mechanical stirrer, adding into a reaction kettle, and forming the soft rubber toy taking the hydrogen bond heat crosslinking gel material as a main body after the potassium chloride solid powder is completely dissolved and crosslinked.
(6) Cooling the formed soft rubber toy taking the hydrogen bond heat crosslinking gel material as a main body to room temperature, then subpackaging the soft rubber toy into four clean 100ml non-porous plastic packaging boxes, placing the packaging boxes into a phi 240mm vacuum drier with an opening, defoaming for 5min under low vacuum, sealing, labeling and packaging the packaging boxes to complete the preparation process of the soft rubber toy, and then storing and transporting the soft rubber toy.
The parameters of the reagent materials selected in the embodiments 1 and 2 of the invention are as follows: 1750 +/-50% of polyvinyl alcohol (Shanghai Yao group-99%); deionized water-made by a laboratory; lithium chloride monohydrate-shanghai national group of pharmaceuticals-analytically pure AR; potassium chloride-Shanghai national drug group-super pure GR; decaglycerol-michelin reagent-98%; potassium sorbate-Shanghai national drug group-chemical pure CP; span-80 (also known as span-80, i.e. emulsifier S-80) -Shanghai national drug group-chemical pure CP; d-limonene (source: orange peel extract) -Maxin reagent-95%; hydrazine yellow (also called lemon yellow, namely food additive acid yellow 23) -Shanghai nationality medicine group-BS.
The gel material which is prepared by the invention and takes nontoxic light metal ions such as lithium ions and potassium ions as the center and takes hydrogen bond thermal crosslinking with polyvinyl alcohol as the framework has the obvious advantages of no toxic and harmful substances, uniform components, less detention, simple preparation method and process, high mechanical automation degree of the preparation process, high cleanliness, low production cost, energy conservation, high efficiency, environmental friendliness, suitability for industrial production and the like.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It is obvious to those skilled in the art that any modification of the present invention, equivalent substitution of the raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. A hydrophilic gel material which takes nontoxic light metal ions as a center and takes hydrogen bond crosslinking as a framework, in particular to a gel material formed by carrying out hydrogen bond thermal crosslinking on polyvinyl alcohol in a water phase by lithium ion auxiliary potassium ions, and is characterized in that the gel material comprises the following main components in percentage by mass:
60 to 75.5 percent of deionized water
1750 +/-50% -15% of polyvinyl alcohol
7.5 to 10 percent of water-soluble lithium ion source (lithium chloride monohydrate, other lithium-containing compounds calculated according to the molar mass ratio of the lithium ions)
5 to 7.5 percent of water-soluble potassium ion source (potassium chloride, and other potassium-containing compounds calculated according to the molar mass ratio of potassium ions)
2. The hydrophilic gel material which is centered on nontoxic light metal ions and takes hydrogen bond crosslinking as a framework as claimed in claim 1, wherein the gel main body comprises the following components in percentage by mass:
deionized water 75.5%
1750 +/-50.5 percent of polyvinyl alcohol
7.5% of water-soluble lithium ion source (lithium chloride monohydrate, other lithium-containing compounds calculated according to the molar mass ratio of lithium ions)
Water-soluble potassium ion source (potassium chloride, other potassium-containing compounds calculated by potassium ion molar mass ratio) 7.5%
3. A hydrogen bonding thermal crosslinking preparation process of the hydrophilic gel material which is centered on nontoxic light metal ions and takes hydrogen bonding crosslinking as a framework according to claim 1, characterized in that the method comprises the following steps:
(1) At normal pressure and 70-95 deg.c, PVA is dissolved in deionized water to form PVA colloid, rather than formaldehyde, its water solution or hydrochloric acid as solvent.
(2) The polyvinyl alcohol colloid is preliminarily crosslinked by using a water-soluble lithium ion source (lithium chloride monohydrate) at the temperature of between 80 and 90 ℃ under normal pressure to form the polyvinyl alcohol colloid.
(3) The gel material is obtained by completely crosslinking polyvinyl alcohol glue solution by using a water-soluble potassium ion source (potassium chloride) at the temperature of between 60 and 80 ℃ under normal pressure.
(4) If the polyvinyl alcohol glue solution does not form gel, reduced pressure distillation at 70-90 ℃ can be adopted to promote the generation of the gel material.
4. A process for preparing hydrobond thermal crosslinking as defined in claim 3, characterized in that said process comprises the following steps:
(1) The polyvinyl alcohol is dissolved in deionized water at 92 deg.C and normal pressure to form polyvinyl alcohol colloid, and formaldehyde and its aqueous solution or hydrochloric acid are not used as solvent.
(2) The polyvinyl alcohol colloid was preliminarily crosslinked at 85 ℃ under normal pressure using a water-soluble lithium ion source (lithium chloride monohydrate) to form a polyvinyl alcohol colloid solution.
(3) The polyvinyl alcohol glue solution is completely crosslinked by using a water-soluble potassium ion source (potassium chloride) at the temperature of 70 ℃ under normal pressure to obtain the gel material.
(4) If the polyvinyl alcohol glue solution does not form gel, a method of reduced pressure distillation at 87 ℃ can be adopted to promote the generation of the gel material.
5. A process for preparing a soft rubber toy by using the hydrophilic gel material which is centered on nontoxic light metal ions and takes hydrogen bond crosslinking as a framework as the main body as the claim 1, which is characterized by comprising the following steps:
(1) The required deionized water, polyvinyl alcohol 1750 +/-50, water-soluble lithium ion source (lithium chloride monohydrate), water-soluble potassium ion source (potassium chloride), water-retaining agent, bacteriostatic agent, emulsifier, aromatizing agent and colorant are calculated and obtained in advance according to the mass percentage of the gel main components.
(2) The polyvinyl alcohol is dissolved in deionized water at 70-95 deg.c and normal pressure to form polyvinyl alcohol colloid without using formaldehyde, water solution or hydrochloric acid as solvent.
(3) The polyvinyl alcohol colloid is preliminarily crosslinked by using a water-soluble lithium ion source (lithium chloride monohydrate) at the temperature of between 80 and 90 ℃ under normal pressure to form the polyvinyl alcohol colloid.
(4) Adding 1 percent of decaglycerol by mass as a water-retaining agent into the preliminarily crosslinked polyvinyl alcohol glue solution.
(5) And adding 1% by mass of potassium sorbate as a bacteriostatic agent into the preliminarily crosslinked polyvinyl alcohol glue solution.
(6) And adding 1 percent of emulsifier for cosmetics in percentage by mass into the preliminarily crosslinked polyvinyl alcohol glue solution to serve as an emulsifier.
(7) Adding 0.5 percent of natural spice extract or edible essence by mass percent into the preliminarily crosslinked polyvinyl alcohol glue solution to be used as a flavoring agent.
(8) Adding 0.2 percent of water-soluble edible pigment by mass percentage into the preliminarily crosslinked polyvinyl alcohol glue solution to be used as a coloring agent.
(9) The polyvinyl alcohol glue solution is completely cross-linked by using a water-soluble potassium ion source (potassium chloride) at the temperature of between 60 and 80 ℃ under normal pressure to obtain the gel material, and if the polyvinyl alcohol glue solution does not form gel, the gel material can be promoted to generate by adopting a reduced pressure distillation method at the temperature of between 70 and 90 ℃, so that the soft rubber toy taking the hydrophilic gel material which takes the nontoxic light metal ions as the center and takes hydrogen bond cross-linking as the framework as the main body is formed.
(10) Cooling the soft rubber toy to normal temperature, defoaming in vacuum, adding appropriate amount of other solid toys or decorative particles compatible and compatible with the soft rubber toy components as filler, subpackaging in container, sealing, labeling and packaging.
6. The process for preparing the soft gum toy according to claim 5, wherein the method comprises the following steps:
(1) The required deionized water, polyvinyl alcohol 1750 +/-50, water-soluble lithium ion source (lithium chloride monohydrate), water-soluble potassium ion source (potassium chloride), water-retaining agent, bacteriostatic agent, emulsifier, aromatizing agent and colorant are calculated and obtained in advance according to the mass percentage of the gel main components.
(2) The polyvinyl alcohol is dissolved in deionized water at the temperature between normal pressure and 92 ℃ to form polyvinyl alcohol colloid, and formaldehyde and aqueous solution thereof or hydrochloric acid and the like are not used as solvents.
(3) The polyvinyl alcohol colloid is preliminarily crosslinked by using a water-soluble lithium ion source (lithium chloride monohydrate) at a temperature between normal pressure and 85 ℃ to form the polyvinyl alcohol colloid.
(4) Adding 1 percent of decaglycerol by mass as a water-retaining agent into the preliminarily crosslinked polyvinyl alcohol glue solution.
(5) And adding 1% by mass of potassium sorbate as a bacteriostatic agent into the preliminarily crosslinked polyvinyl alcohol glue solution.
(6) And adding 1 percent of emulsifier for cosmetics in percentage by mass into the preliminarily crosslinked polyvinyl alcohol glue solution to serve as an emulsifier.
(7) Adding natural essence or edible essence as perfuming agent in the mass percent of 0.5% into the preliminarily crosslinked polyvinyl alcohol glue solution.
(8) Adding 0.2 percent of water-soluble edible pigment by mass percentage into the preliminarily crosslinked polyvinyl alcohol glue solution to be used as a coloring agent.
(9) The gel material is obtained by completely crosslinking polyvinyl alcohol glue solution by using a water-soluble potassium ion source (potassium chloride) at the temperature between normal pressure and 70 ℃, if the polyvinyl alcohol glue solution does not form gel, the gel material can be promoted to generate by adopting a method of reduced pressure distillation at 87 ℃, and then the soft rubber toy taking the hydrophilic gel material which takes the nontoxic light metal ions as the center and takes hydrogen bond crosslinking as a framework as the main body is formed.
(10) Cooling the soft rubber toy to normal temperature, defoaming in vacuum, adding other solid toys or decorative particles compatible and conforming with the soft rubber toy components as filler, sealing, packaging and labeling.
7. Preferably, the non-toxic light metal ion-centered, hydrogen-bond cross-linked hydrophilic gel material of claims 1-2 is formed by using non-toxic light metal ions such as lithium ions and potassium ions as centers and hydrogen-bond cross-linking with polyvinyl alcohol as a skeleton, rather than ester-bond cross-linking with polyacid as a skeleton, i.e., the non-toxic light metal ion-centered, hydrogen-bond cross-linked hydrophilic gel material of claims 1-2 and the hydrogen-bond thermal cross-linking preparation process of claims 3-4 and the soft gel toy preparation process of claim 5 do not contain or involve sodium tetraborate (i.e., borax), formaldehyde and their aqueous solutions and other national standards listed in the current national standard "GB 6675: migration elements in toy safety.
8. Preferably, the hydrophilic gel material centered on nontoxic light metal ions and having hydrogen bond crosslinking as a skeleton according to claims 1-2 and the hydrogen bond thermal crosslinking preparation process according to claims 3-4 are each compatible with at least one or more of water-retaining agent, bacteriostatic agent, emulsifier, aromatizing agent, coloring agent and their equivalent substitutes and constitute the soft gel toy according to claims 5-6, and an appropriate amount of other solid toys or decorative particles compatible and compatible with the soft gel toy components and their equivalent substitutes can be added to the soft gel toy as a filler.
9. Preferably, the water-retaining agent decaglycerol used in the process for preparing a soft rubber toy as described in claims 5 to 6 is a polyether other than polyol, which is not easily crosslinked with boric acid to form borate and has strong hydrophilicity to reduce the residue of toy components while retaining water lubrication.
10. Preferably, the soft rubber toy obtained in the process for preparing the soft rubber toy as claimed in claims 5 to 6 has good mechanical properties, and can withstand high-strength mechanical operations such as pulling and beating when the toy is reasonably abused; because the gel material takes nontoxic light metal ions such as lithium ions and potassium ions as the center and takes hydrogen bond crosslinking with polyvinyl alcohol as a framework, the gel material can self-repair intramolecular damage caused by hydrogen bond fracture in a water retention static state for several hours to several days after being subjected to mechanical operation.
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