CN117924659A - Creep-resistant composite material and application thereof in tooth socket - Google Patents
Creep-resistant composite material and application thereof in tooth socket Download PDFInfo
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- CN117924659A CN117924659A CN202410100986.3A CN202410100986A CN117924659A CN 117924659 A CN117924659 A CN 117924659A CN 202410100986 A CN202410100986 A CN 202410100986A CN 117924659 A CN117924659 A CN 117924659A
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- castor oil
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- silicon dioxide
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- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 210000003781 tooth socket Anatomy 0.000 title abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000004359 castor oil Substances 0.000 claims abstract description 70
- 235000019438 castor oil Nutrition 0.000 claims abstract description 70
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims abstract description 70
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 58
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000003756 stirring Methods 0.000 claims abstract description 55
- 238000002360 preparation method Methods 0.000 claims abstract description 46
- 238000002156 mixing Methods 0.000 claims abstract description 45
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000010438 heat treatment Methods 0.000 claims abstract description 40
- 229920003043 Cellulose fiber Polymers 0.000 claims abstract description 29
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 29
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 20
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 19
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims abstract description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 58
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 34
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 30
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical group C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000007822 coupling agent Substances 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 22
- 235000002906 tartaric acid Nutrition 0.000 claims description 22
- 239000011975 tartaric acid Substances 0.000 claims description 22
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 19
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 19
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 19
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000005642 Oleic acid Substances 0.000 claims description 19
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 19
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 19
- 239000004408 titanium dioxide Substances 0.000 claims description 17
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 244000028419 Styrax benzoin Species 0.000 claims description 15
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 15
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 15
- 229960002130 benzoin Drugs 0.000 claims description 15
- 235000019382 gum benzoic Nutrition 0.000 claims description 15
- FETFXNFGOYOOSP-UHFFFAOYSA-N 1-sulfanylpropan-2-ol Chemical compound CC(O)CS FETFXNFGOYOOSP-UHFFFAOYSA-N 0.000 claims description 14
- 238000009210 therapy by ultrasound Methods 0.000 claims description 14
- 238000004108 freeze drying Methods 0.000 claims description 10
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 238000002390 rotary evaporation Methods 0.000 claims description 8
- RVEZZJVBDQCTEF-UHFFFAOYSA-N sulfenic acid Chemical compound SO RVEZZJVBDQCTEF-UHFFFAOYSA-N 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 27
- 229920002635 polyurethane Polymers 0.000 abstract description 26
- 239000004814 polyurethane Substances 0.000 abstract description 26
- 238000004132 cross linking Methods 0.000 abstract description 7
- 230000001965 increasing effect Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 19
- 230000001678 irradiating effect Effects 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229920002678 cellulose Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000012937 correction Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- 241001330002 Bambuseae Species 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011425 bamboo Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6484—Polysaccharides and derivatives thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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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)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a creep-resistant composite material and application thereof in tooth sockets, belonging to the technical field of tooth sockets. The preparation method of the composite material comprises the following steps: placing polytetrahydrofuran ether glycol, modified castor oil, modified cellulose fiber, 1, 4-butanediol and other auxiliary agents into a reaction kettle, heating, stirring and mixing, adding 4,4' -diphenylmethane diisocyanate for reaction, adding modified silicon dioxide for continuous reaction, heating and heating up, and curing to obtain a composite material; through modifying castor oil and silicon dioxide, a compact structure is formed by increasing the crosslinking density of each component in the reaction process, so that the stability of the polyurethane material is improved, and the creep resistance of the polyurethane material is enhanced.
Description
Technical Field
The invention belongs to the technical field of dental braces, and relates to a creep-resistant composite material and application thereof in dental braces.
Background
When the tooth socket is worn, the tooth socket can apply correction force to the teeth, and as the invisible tooth socket is made of medical grade plastic, the correction force applied to the teeth by the invisible tooth socket can be gradually reduced due to the creep effect of the material, so that the correction effect of the teeth is affected. Creep effects, also known as creep modulus, vary from material to material due to a number of factors, such as the degree of force applied, temperature, time, and environmental factors. With time, the creep modulus of the material is reduced, and the greater the stress level, the higher the creep modulus reduction speed.
Polyurethanes can degrade under the influence of various environmental factors, the degradation behavior of the polyurethane being dependent on the chemical structure of the polyurethane backbone, on the nature and chemical composition of the hard and soft segments used, in particular the type of soft segment (polyol). Under normal use conditions, degradation behavior of polyurethane results in loss of desirable properties (e.g., elasticity, tensile strength, color and shape), most directly resulting in shortened service life of polyurethane materials.
Castor oil, a natural vegetable oil, has a specific chemical structure such that the hydroxyl groups therein are very uniformly distributed. This uniformity plays a key role in the polyurethane synthesis process, as it enables the polyurethane to eventually form a crosslinked structure that is very uniform. Polyurethanes based on castor oil modification have significantly higher thermal stability and mechanical strength than other seed oil based polyurethanes.
Polyurethanes modified based on castor oil are prepared mainly by two main routes. The first route is to crosslink the polyurethane by the polyhydroxy character of castor oil, in such a way that the mechanical properties and thermal stability of the polyurethane can be significantly enhanced. The second route is to synthesize bio-based polyols with different molecular structures by modifying the polyhydroxy or double bonds of castor oil. These polyols are further used for the synthesis of functional polyurethanes, expanding the range of applications of polyurethanes.
Disclosure of Invention
The invention aims to provide a creep-resistant composite material and application thereof in dental braces, wherein castor oil and silicon dioxide are modified, and a compact structure is formed by increasing the crosslinking density of each component in the reaction process, so that the stability of a polyurethane material is improved, and the creep-resistant performance of the polyurethane material is enhanced.
The aim of the invention can be achieved by the following technical scheme:
A creep-resistant composite material, the method of making the composite material comprising the steps of:
placing polytetrahydrofuran ether glycol, modified castor oil, modified cellulose fiber, 1, 4-butanediol and other auxiliary agents into a reaction kettle, heating, stirring and mixing, adding 4,4' -diphenylmethane diisocyanate for reaction, adding modified silicon dioxide for continuous reaction, heating and heating up, and curing to obtain a composite material;
The preparation method of the modified castor oil comprises the following steps:
Stirring and mixing castor oil, mercapto-alcohol, photoinitiator and methylene dichloride in a container, and washing, drying and evaporating solvent after ultraviolet treatment to obtain modified castor oil;
the preparation method of the modified silicon dioxide comprises the following steps:
1) Stirring and mixing oleic acid, 3-mercaptopropyl triethoxysilane and a photoinitiator, and performing ultraviolet irradiation treatment to obtain a modified coupling agent;
2) And (3) stirring and mixing absolute ethyl alcohol, deionized water and silicon dioxide, regulating the pH value, performing ultrasonic treatment, adding a modified coupling agent, heating and stirring, and performing primary drying, washing and secondary drying to obtain the modified silicon dioxide.
As a preferable technical scheme of the invention, in the preparation method of the modified castor oil, the stirring and mixing time is 5-10min; the ultraviolet treatment condition is that the ultraviolet irradiation is carried out for 2.0 to 2.5 hours at the temperature of 35 to 40 ℃; the washing condition is that saturated sodium chloride and distilled water are adopted for washing for 3 times; the drying condition is that anhydrous magnesium sulfate is adopted for drying; the conditions for evaporating the solvent are such that the dichloromethane is removed by rotary evaporation.
In a preferred embodiment of the present invention, in the preparation method of modified castor oil, the mercapto-alcohol is one or both of 2-mercaptoethanol and 1-mercapto-2-propanol; the photoinitiator is benzoin dimethyl ether; the mass ratio of the castor oil to the mercapto-alcohol to the photoinitiator to the dichloromethane is 90:8-10:1-1.5:50-60; in the scheme of the invention, when castor oil containing a plurality of hydroxyl groups is added, hydroxyl functional groups in the castor oil react with other components of the polyurethane system to form cross-linked structures, and the cross-linked structures can strengthen a polymer network of the material and improve the strength and the stability of the material, so that the creep resistance of the material is improved.
As a preferable technical scheme of the invention, in the preparation method of the composite material, the heating temperature is 60-80 ℃; the stirring and mixing conditions are that stirring is carried out for 3-8min at the rotating speed of 300-400 r/min; the reaction condition is that the reaction is carried out for 2min at 70-80 ℃; the condition of the continuous reaction is that the reaction is carried out for 3min at 70-80 ℃; the heating temperature is raised to 100-105 ℃ at a heating speed of 5-10 ℃/min; the curing condition is curing for 4-6 hours at 95-100 ℃.
As a preferred technical scheme of the invention, in the preparation method of the composite material, the molecular weight of the polytetrahydrofuran ether glycol is 1000; the mass ratio of the polytetrahydrofuran ether glycol, the modified castor oil, the 1, 4-butanediol, the 4,4' -diphenylmethane diisocyanate, the modified silicon dioxide, the modified cellulose fiber and other auxiliary agents is 80-100:10-15:12-22:66.5-90.0:4-9:3-8:2.5-3.0, in the scheme of the invention, the modified cellulose fiber has high hydrophilicity and crosslinking activity, can form a composite material with polyurethane, and the crosslinking structure can increase the elongation at break and toughness of the material, thereby enhancing the creep resistance of the material; in addition, the modified cellulose fiber can also increase the viscosity and the viscosity of the material and improve the stability of the material.
As a preferred technical scheme of the invention, the preparation method of the modified cellulose fiber comprises the following steps:
(1) Crushing, drying and grinding bamboo pulp to obtain cellulose particles;
(2) Mixing cellulose particles with sodium hydroxide aqueous solution with the concentration of 0.8mol/L according to the mass ratio of 3:110, ultrasonic treatment for 40min, dialysis for 3d and freeze drying to obtain the modified cellulose fiber.
As a preferred technical scheme of the invention, in the step 1), the mass ratio of oleic acid to 3-mercaptopropyl triethoxysilane to photoinitiator is 28-30:20-22.5:1.1 to 1.6; the ultraviolet irradiation treatment condition is that irradiation is carried out for 20-25h under 365nm and 1400 mW; in the scheme of the invention, oleic acid serves as a chain extender in the preparation of polyurethane, so that a longer polyurethane chain can be formed, the molecular weight of polyurethane is increased, and the polyurethane has better mechanical properties including tensile strength and elongation at break; in addition, the addition of oleic acid can also improve the thermal stability and creep resistance of the material.
Further, the modified silicon dioxide can be crosslinked with polyurethane chains to form a three-dimensional network structure, so that the strength and hardness of the material can be enhanced, and the stretch-breaking resistance of the material is improved, thereby enhancing the creep resistance of the material; in addition, the modified silica can increase the viscosity and viscosity of the material through filling action, so that the material is more stable.
As a preferable technical scheme of the invention, in the step 2), the stirring and mixing conditions are that stirring and mixing are carried out for 5-10min under 200-300 r/min; the pH value is adjusted to 8.5-9.0; the condition of ultrasonic treatment is that the ultrasonic treatment is carried out for 30-45min under 600-650W; the heating and stirring conditions are that stirring is carried out for 10-15 hours at the temperature of 58.5-60 ℃ and the rotating speed of 300-450 r/min; the primary drying condition is that drying is carried out at 80 ℃; the washing is carried out for 3 times by adopting alcohol washing; the secondary drying is freeze drying.
As a preferable technical scheme of the invention, in the step 2), the dosage ratio of the absolute ethyl alcohol, the deionized water, the silicon dioxide and the modified coupling agent is 100-110mL:1mL:5.0-5.5g:4.5g.
As a preferable technical scheme of the invention, the other auxiliary agent is formed by mixing titanium dioxide and tartaric acid; the mass ratio of the titanium dioxide to the tartaric acid is 1.0-2.0:3.5; in the scheme of the invention, tartaric acid is a bio-based carboxylic acid, and compared with a linear dihydroxy chain extender, tartaric acid is a polyhydroxy small molecule, so that the reaction of hydroxyl on the structure of tartaric acid and isocyanate further increases the crosslinking degree, and finally a material with higher thermal stability is synthesized; that is, tartaric acid can promote the crosslinking reaction of polyurethane to form a more compact polymer network, enhance the tensile strength of the material and effectively enhance the creep resistance of the material.
As a preferred embodiment of the present application, all photoinitiators used in all examples and comparative examples of the present application are benzoin dimethyl ether.
The invention discloses an application of a creep-resistant composite material, which is applied to a dental mouthpiece.
The invention has the beneficial effects that:
According to the invention, castor oil and silicon dioxide are modified, and a compact structure is formed by increasing the crosslinking density of each component in the reaction process, so that the stability of the material is improved, and the creep resistance of the material is enhanced.
Detailed Description
In order to further describe the technical means and effects adopted by the present invention for achieving the intended purpose, the following detailed description is given below with reference to the embodiments, structures, features and effects according to the present invention.
The modified cellulose fibers used in examples 1 to 10 and comparative examples 1 to 7 were each produced by the following production process;
The preparation method of the modified cellulose fiber comprises the following steps:
1) Crushing, drying and grinding bamboo pulp to obtain cellulose particles;
2) Mixing cellulose particles with sodium hydroxide aqueous solution with the concentration of 0.8mol/L according to the mass ratio of 3:110, ultrasonic treatment for 40min, dialysis for 3d and freeze drying to obtain the modified cellulose fiber.
Example 1
A preparation method of the creep-resistant composite material comprises the following steps:
Placing polytetrahydrofuran ether glycol, modified castor oil, modified cellulose fiber, 1, 4-butanediol and other auxiliary agents into a reaction kettle, heating to 60 ℃, stirring for 3min at the rotating speed of 300r/min, adding 4,4' -diphenylmethane diisocyanate, reacting for 2min at 70 ℃, adding modified silicon dioxide, continuously reacting for 3min at 70 ℃, heating to 100 ℃ at the heating speed of 5 ℃/min, and curing for 4h at 95 ℃ to obtain a composite material;
Wherein the molecular weight of the polytetrahydrofuran ether glycol is 1000; the mass ratio of polytetrahydrofuran ether glycol, modified castor oil, 1, 4-butanediol, 4' -diphenylmethane diisocyanate, modified silicon dioxide, modified cellulose fiber and other auxiliary agents is 80:10:12:66.5:4:3:2.5; the other auxiliary agent is formed by mixing titanium dioxide and tartaric acid; the mass ratio of the titanium dioxide to the tartaric acid is 1.0:3.5.
The preparation method of the modified castor oil comprises the following steps:
Placing castor oil, 1-mercapto-2-propanol, benzoin dimethyl ether and methylene dichloride in a container, stirring and mixing for 5min, irradiating for 2.0h at 35 ℃, washing for 3 times by using saturated sodium chloride and distilled water, drying by using anhydrous magnesium sulfate, and removing the methylene dichloride by adopting rotary evaporation to obtain modified castor oil; wherein, the mass ratio of the castor oil to the 1-mercapto-2-propanol to the benzoin dimethyl ether to the dichloromethane is 90:8:1:50.
The preparation method of the modified silicon dioxide comprises the following steps:
1) Stirring and mixing oleic acid, 3-mercaptopropyl triethoxysilane and a photoinitiator, and irradiating for 20 hours at 365nm and 1400mW to obtain a modified coupling agent; wherein the mass ratio of the oleic acid to the 3-mercaptopropyl triethoxysilane to the photoinitiator is 28:20:1.1;
2) Mixing absolute ethyl alcohol, deionized water and silicon dioxide for 5min under 200r/min, regulating the pH value to 8.5, carrying out ultrasonic treatment for 30min under 600W, adding a modified coupling agent, drying at 80 ℃ after stirring for 10h under the temperature of 58.5 ℃ and the rotating speed of 300r/min, washing for 3 times by adopting alcohol, and freeze-drying to obtain modified silicon dioxide; wherein, the dosage ratio of the absolute ethyl alcohol, the deionized water, the silicon dioxide and the modified coupling agent is 100mL:1mL:5.0g:4.5g.
Example 2
A preparation method of the creep-resistant composite material comprises the following steps:
Placing polytetrahydrofuran ether glycol, modified castor oil, modified cellulose fiber, 1, 4-butanediol and other auxiliary agents into a reaction kettle, heating to 64 ℃, stirring for 4min at a speed of 320r/min, adding 4,4' -diphenylmethane diisocyanate, reacting for 2min at 72 ℃, adding modified silicon dioxide, continuously reacting for 3min at 72 ℃, heating to 101 ℃ at a heating speed of 6 ℃/min, and curing for 4.4h at 96 ℃ to obtain a composite material;
Wherein the molecular weight of the polytetrahydrofuran ether glycol is 1000; the mass ratio of the polytetrahydrofuran ether glycol, the modified castor oil, the 1, 4-butanediol, the 4,4' -diphenylmethane diisocyanate, the modified silicon dioxide, the modified cellulose fiber and other auxiliary agents is 84:11:14:71.2:5:4:2.6; the other auxiliary agent is formed by mixing titanium dioxide and tartaric acid; the mass ratio of the titanium dioxide to the tartaric acid is 1.2:3.5.
The preparation method of the modified castor oil comprises the following steps:
placing castor oil, 1-mercapto-2-propanol, benzoin dimethyl ether and methylene dichloride in a container, stirring and mixing for 6min, irradiating for 2.1h at 36 ℃ with ultraviolet rays, washing for 3 times with saturated sodium chloride and distilled water, drying with anhydrous magnesium sulfate, and removing methylene dichloride by rotary evaporation to obtain modified castor oil; wherein, the mass ratio of the castor oil to the 1-mercapto-2-propanol to the benzoin dimethyl ether to the dichloromethane is 90:8.4:1.1:52.
The preparation method of the modified silicon dioxide comprises the following steps:
1) Stirring and mixing oleic acid, 3-mercaptopropyl triethoxysilane and a photoinitiator, and irradiating for 21 hours at 365nm and 1400mW to obtain a modified coupling agent; wherein the mass ratio of the oleic acid to the 3-mercaptopropyl triethoxysilane to the photoinitiator is 28.4:20.5:1.2;
2) Mixing absolute ethyl alcohol, deionized water and silicon dioxide for 6min at 220r/min under stirring, regulating the pH value to 8.6, performing ultrasonic treatment for 33min at 610W, adding a modified coupling agent, stirring for 11h at the temperature of 58.8 ℃ at the rotating speed of 330r/min, drying at 80 ℃, washing with alcohol for 3 times, and performing freeze drying to obtain modified silicon dioxide; wherein, the dosage ratio of the absolute ethyl alcohol, the deionized water, the silicon dioxide and the modified coupling agent is 102mL:1mL:5.1g:4.5g.
Example 3
A preparation method of the creep-resistant composite material comprises the following steps:
placing polytetrahydrofuran ether glycol, modified castor oil, modified cellulose fiber, 1, 4-butanediol and other auxiliary agents into a reaction kettle, heating to 68 ℃, stirring for 5min at the speed of 340r/min, adding 4,4' -diphenylmethane diisocyanate, reacting for 2min at 74 ℃, adding modified silicon dioxide, continuously reacting for 3min at 74 ℃, heating to 102 ℃ at the heating speed of 7 ℃/min, and curing for 4.8h at 97 ℃ to obtain a composite material;
Wherein the molecular weight of the polytetrahydrofuran ether glycol is 1000; the mass ratio of the polytetrahydrofuran ether glycol, the modified castor oil, the 1, 4-butanediol, the 4,4' -diphenylmethane diisocyanate, the modified silicon dioxide, the modified cellulose fiber and other auxiliary agents is 88:12:16:75.9:6:5:2.7; the other auxiliary agent is formed by mixing titanium dioxide and tartaric acid; the mass ratio of the titanium dioxide to the tartaric acid is 1.4:3.5.
The preparation method of the modified castor oil comprises the following steps:
Placing castor oil, 1-mercapto-2-propanol, benzoin dimethyl ether and methylene dichloride in a container, stirring and mixing for 7min, irradiating for 2.2h at 37 ℃, washing for 3 times by using saturated sodium chloride and distilled water, drying by using anhydrous magnesium sulfate, and removing the methylene dichloride by adopting rotary evaporation to obtain modified castor oil; wherein, the mass ratio of the castor oil to the 1-mercapto-2-propanol to the benzoin dimethyl ether to the dichloromethane is 90:8.8:1.2:54.
The preparation method of the modified silicon dioxide comprises the following steps:
1) Stirring and mixing oleic acid, 3-mercaptopropyl triethoxysilane and a photoinitiator, and irradiating for 22 hours at 365nm and 1400mW to obtain a modified coupling agent; wherein the mass ratio of the oleic acid to the 3-mercaptopropyl triethoxysilane to the photoinitiator is 28.8:21:1.3;
2) Mixing absolute ethyl alcohol, deionized water and silicon dioxide for 7min at 240r/min under stirring, regulating the pH value to 8.7, performing ultrasonic treatment for 36min at 620W, adding a modified coupling agent, stirring for 12h at 360r/min at 59.1 ℃, drying at 80 ℃, washing with alcohol for 3 times, and freeze-drying to obtain modified silicon dioxide; wherein, the dosage ratio of the absolute ethyl alcohol, the deionized water, the silicon dioxide and the modified coupling agent is 104mL:1mL:5.2g:4.5g.
Example 4
A preparation method of the creep-resistant composite material comprises the following steps:
Placing polytetrahydrofuran ether glycol, modified castor oil, modified cellulose fiber, 1, 4-butanediol and other auxiliary agents into a reaction kettle, heating to 72 ℃, stirring at 360r/min for 6min, adding 4,4' -diphenylmethane diisocyanate, reacting for 2min at 76 ℃, adding modified silicon dioxide, continuously reacting for 3min at 76 ℃, heating to 103 ℃ at a heating rate of 8 ℃/min, and curing at 98 ℃ for 5.2h to obtain a composite material;
wherein the molecular weight of the polytetrahydrofuran ether glycol is 1000; the mass ratio of polytetrahydrofuran ether glycol, modified castor oil, 1, 4-butanediol, 4' -diphenylmethane diisocyanate, modified silicon dioxide, modified cellulose fiber and other auxiliary agents is 92:13:18:80.6:7:6:2.8; the other auxiliary agent is formed by mixing titanium dioxide and tartaric acid; the mass ratio of the titanium dioxide to the tartaric acid is 1.6:3.5.
The preparation method of the modified castor oil comprises the following steps:
Placing castor oil, 1-mercapto-2-propanol, benzoin dimethyl ether and methylene dichloride in a container, stirring and mixing for 8min, irradiating for 2.3h at 38 ℃, washing for 3 times by using saturated sodium chloride and distilled water, drying by using anhydrous magnesium sulfate, and removing the methylene dichloride by adopting rotary evaporation to obtain modified castor oil; wherein, the mass ratio of the castor oil to the 1-mercapto-2-propanol to the benzoin dimethyl ether to the dichloromethane is 90:9.2:1.3:56.
The preparation method of the modified silicon dioxide comprises the following steps:
1) Stirring and mixing oleic acid, 3-mercaptopropyl triethoxysilane and a photoinitiator, and irradiating for 23 hours at 365nm and 1400mW to obtain a modified coupling agent; wherein the mass ratio of the oleic acid to the 3-mercaptopropyl triethoxysilane to the photoinitiator is 29.2:21.5:1.4;
2) Mixing absolute ethyl alcohol, deionized water and silicon dioxide for 8min at 260r/min under stirring, regulating the pH value to 8.8, carrying out ultrasonic treatment at 630W for 39min, adding a modified coupling agent, drying at 80 ℃ after stirring for 13h at 59.4 ℃ and 390r/min, washing for 3 times by adopting alcohol, and freeze-drying to obtain modified silicon dioxide; wherein, the dosage ratio of the absolute ethyl alcohol, the deionized water, the silicon dioxide and the modified coupling agent is 106mL:1mL:5.3g:4.5g.
Example 5
A preparation method of the creep-resistant composite material comprises the following steps:
placing polytetrahydrofuran ether glycol, modified castor oil, modified cellulose fiber, 1, 4-butanediol and other auxiliary agents into a reaction kettle, heating to 76 ℃, stirring for 7min at 380r/min, adding 4,4' -diphenylmethane diisocyanate, reacting for 2min at 78 ℃, adding modified silicon dioxide, continuously reacting for 3min at 78 ℃, heating to 104 ℃ at a heating rate of 9 ℃/min, and curing for 5.6h at 99 ℃ to obtain a composite material;
Wherein the molecular weight of the polytetrahydrofuran ether glycol is 1000; the mass ratio of the polytetrahydrofuran ether glycol, the modified castor oil, the 1, 4-butanediol, the 4,4' -diphenylmethane diisocyanate, the modified silicon dioxide, the modified cellulose fiber and other auxiliary agents is 96:14:20:85.3:8:7:2.9; the other auxiliary agent is formed by mixing titanium dioxide and tartaric acid; the mass ratio of the titanium dioxide to the tartaric acid is 1.8:3.5.
The preparation method of the modified castor oil comprises the following steps:
placing castor oil, 1-mercapto-2-propanol, benzoin dimethyl ether and methylene dichloride in a container, stirring and mixing for 9min, irradiating for 2.4h at 39 ℃, washing for 3 times by using saturated sodium chloride and distilled water, drying by using anhydrous magnesium sulfate, and removing the methylene dichloride by adopting rotary evaporation to obtain modified castor oil; wherein, the mass ratio of the castor oil to the 1-mercapto-2-propanol to the benzoin dimethyl ether to the dichloromethane is 90:9.6:1.4:58.
The preparation method of the modified silicon dioxide comprises the following steps:
1) Stirring and mixing oleic acid, 3-mercaptopropyl triethoxysilane and a photoinitiator, and irradiating for 24 hours at 365nm and 1400mW to obtain a modified coupling agent; wherein the mass ratio of the oleic acid to the 3-mercaptopropyl triethoxysilane to the photoinitiator is 29.6:22:1.5;
2) Mixing absolute ethyl alcohol, deionized water and silicon dioxide for 9min at 280r/min under stirring, regulating the pH value to 8.9, performing ultrasonic treatment at 640W for 42min, adding a modified coupling agent, stirring for 14h at the temperature of 59.7 ℃ at the rotating speed of 420r/min, drying at 80 ℃, washing with alcohol for 3 times, and performing freeze drying to obtain modified silicon dioxide; wherein, the dosage ratio of the absolute ethyl alcohol, the deionized water, the silicon dioxide and the modified coupling agent is 108mL:1mL:5.4g:4.5g.
Example 6
A preparation method of the creep-resistant composite material comprises the following steps:
Placing polytetrahydrofuran ether glycol, modified castor oil, modified cellulose fiber, 1, 4-butanediol and other auxiliary agents into a reaction kettle, heating to 80 ℃, stirring for 8min at the rotation speed of 400r/min, adding 4,4' -diphenylmethane diisocyanate, reacting for 2min at 80 ℃, adding modified silicon dioxide, continuously reacting for 3min at 80 ℃, heating to 105 ℃ at the heating speed of 10 ℃/min, and curing for 6h at 100 ℃ to obtain a composite material;
Wherein the molecular weight of the polytetrahydrofuran ether glycol is 1000; the mass ratio of the polytetrahydrofuran ether glycol, the modified castor oil, the 1, 4-butanediol, the 4,4' -diphenylmethane diisocyanate, the modified silicon dioxide, the modified cellulose fiber and other auxiliary agents is 100:15:22:90.0:9:8:3.0; the other auxiliary agent is formed by mixing titanium dioxide and tartaric acid; the mass ratio of the titanium dioxide to the tartaric acid is 2.0:3.5.
The preparation method of the modified castor oil comprises the following steps:
Placing castor oil, 1-mercapto-2-propanol, benzoin dimethyl ether and methylene dichloride in a container, stirring and mixing for 10min, irradiating for 2.5h at 40 ℃, washing for 3 times by using saturated sodium chloride and distilled water, drying by using anhydrous magnesium sulfate, and removing the methylene dichloride by adopting rotary evaporation to obtain modified castor oil; wherein, the mass ratio of the castor oil to the 1-mercapto-2-propanol to the benzoin dimethyl ether to the dichloromethane is 90:10:1.5:60.
The preparation method of the modified silicon dioxide comprises the following steps:
1) Stirring and mixing oleic acid, 3-mercaptopropyl triethoxysilane and a photoinitiator, and irradiating for 25 hours at 365nm and 1400mW to obtain a modified coupling agent; wherein the mass ratio of the oleic acid to the 3-mercaptopropyl triethoxysilane to the photoinitiator is 30:22.5:1.6;
2) Mixing absolute ethyl alcohol, deionized water and silicon dioxide for 10min at 300r/min under stirring, regulating the pH value to 9.0, carrying out ultrasonic treatment for 45min at 650W, adding a modified coupling agent, stirring for 15h at the temperature of 60 ℃ at the rotating speed of 450r/min, drying at 80 ℃, washing with alcohol for 3 times, and freeze-drying to obtain modified silicon dioxide; wherein, the dosage ratio of the absolute ethyl alcohol, the deionized water, the silicon dioxide and the modified coupling agent is 110mL:1mL:5.5g:4.5g.
Example 7
The difference compared with example 4 is that the mass ratio of polytetrahydrofuran ether glycol, modified castor oil, 1, 4-butanediol, 4' -diphenylmethane diisocyanate, modified silica, modified cellulose fiber and other auxiliary agent is 92:15:18:80.6:7:6:2.8, the rest components, the preparation steps and the parameters are consistent.
Example 8
The difference compared with example 4 is that the mass ratio of polytetrahydrofuran ether glycol, modified castor oil, 1, 4-butanediol, 4' -diphenylmethane diisocyanate, modified silica, modified cellulose fiber and other auxiliary agent is 92:13:18:80.6:9:6:2.8, the rest components, the preparation steps and the parameters are consistent.
Example 9
The difference compared with example 4 is that the mass ratio of polytetrahydrofuran ether glycol, modified castor oil, 1, 4-butanediol, 4' -diphenylmethane diisocyanate, modified silica, modified cellulose fiber and other auxiliary agent is 92:13:18:80.6:7:8:2.8, the rest components, the preparation steps and the parameters are consistent.
Example 10
The difference compared to example 4 is that the mass ratio of titanium dioxide to tartaric acid is 1.6:3.6, the rest components, the preparation steps and the parameters are consistent.
Comparative example 1
In comparison with example 4, the difference is that comparative example 1 uses castor oil instead of modified castor oil, and the remaining components, preparation steps and parameters are identical.
Comparative example 2
In comparison with example 4, comparative example 2 uses 1, 4-butanediol instead of modified castor oil, the remaining components, preparation steps and parameters being identical.
Comparative example 3
In comparison with example 4, the difference is that comparative example 3 does not use oleic acid, and the remaining components, preparation steps and parameters are identical.
Comparative example 4
In comparison with example 4, comparative example 4 uses silica instead of modified silica, and the remaining components, preparation steps and parameters are identical.
Comparative example 5
In comparison with example 4, the difference is that comparative example 5 does not modify the cellulose fiber, and the remaining components, preparation steps and parameters are identical.
Comparative example 6
In comparison with example 4, the difference is that comparative example 6 does not use tartaric acid, and the remaining components, preparation steps and parameters are identical.
Comparative example 7
The difference compared with example 4 is that the order of addition of the modified silica of comparative example 7 is different;
A preparation method of the creep-resistant composite material comprises the following steps:
Placing polytetrahydrofuran ether glycol, modified castor oil, modified cellulose fiber, 1, 4-butanediol, modified silicon dioxide and other auxiliary agents into a reaction kettle, heating to 72 ℃, stirring for 6min at a speed of 360r/min, adding 4,4' -diphenylmethane diisocyanate, reacting for 5min at 76 ℃, heating to 103 ℃ at a heating speed of 8 ℃/min, and curing for 5.2h at 98 ℃ to obtain a composite material;
The other components, the preparation steps and the parameters are consistent.
The composites prepared in examples 1-10 and comparative examples 1-7 were cast into films using a 10% solution, the film thickness was about 1mm, and the specimens were made using a dumbbell-type standard sample knife and the following experiments were performed:
Tensile property test: sample pieces before and after aging treatment are tested on an Instron-5869 type tensile testing machine, the tensile speed is 10mm/min, the number of each sample is 10, and the results are averaged; the test results are shown in Table 1.
Creep test: creep testing was performed by punching holes in each end of the coupon. One end of the coupon was hung with a hook, and a weight of 4.5kg was attached from the other end by another hook. After 24 hours at 85 ℃, the samples were visually inspected. The "pass" scale indicates that no visible movement of one end of the coupon is seen. The "failed" scale indicates movement or failure of one end of the coupon. The test results are shown in Table 1.
TABLE 1
From the test results in Table 1, it is evident that the creep resistance of the composite materials prepared in examples 1 to 10 of the present invention is significantly better than that of comparative examples 1 to 7 in examples 1 to 10 as compared with comparative examples 1 to 7.
The present invention is not limited to the above embodiments, but is capable of modification and variation in detail, and other modifications and variations can be made by those skilled in the art without departing from the scope of the present invention.
Claims (9)
1. A creep-resistant composite material, the method of making the composite material comprising the steps of:
placing polytetrahydrofuran ether glycol, modified castor oil, modified cellulose fiber, 1, 4-butanediol and other auxiliary agents into a reaction kettle, heating, stirring and mixing, adding 4,4' -diphenylmethane diisocyanate for reaction, adding modified silicon dioxide for continuous reaction, heating and heating up, and curing to obtain a composite material;
The preparation method of the modified castor oil comprises the following steps:
Stirring and mixing castor oil, mercapto-alcohol, photoinitiator and methylene dichloride in a container, and washing, drying and evaporating solvent after ultraviolet treatment to obtain modified castor oil;
the preparation method of the modified silicon dioxide comprises the following steps:
1) Stirring and mixing oleic acid, 3-mercaptopropyl triethoxysilane and a photoinitiator, and performing ultraviolet irradiation treatment to obtain a modified coupling agent;
2) And (3) stirring and mixing absolute ethyl alcohol, deionized water and silicon dioxide, regulating the pH value, performing ultrasonic treatment, adding a modified coupling agent, heating and stirring, and performing primary drying, washing and secondary drying to obtain the modified silicon dioxide.
2. A creep resistant composite according to claim 1, wherein: in the preparation method of the modified castor oil, the stirring and mixing time is 5-10min; the ultraviolet treatment condition is that the ultraviolet irradiation is carried out for 2.0 to 2.5 hours at the temperature of 35 to 40 ℃; the washing condition is that saturated sodium chloride and distilled water are adopted for washing for 3 times; the drying condition is that anhydrous magnesium sulfate is adopted for drying; the conditions for evaporating the solvent are such that the dichloromethane is removed by rotary evaporation.
3. A creep resistant composite according to claim 1, wherein: in the preparation method of the modified castor oil, the mercapto-alcohol is one or two of 2-mercapto ethanol and 1-mercapto-2-propanol; the photoinitiator is benzoin dimethyl ether; the mass ratio of the castor oil to the mercapto-alcohol to the photoinitiator to the dichloromethane is 90:8-10:1-1.5:50-60.
4. A creep resistant composite according to claim 1, wherein: in the preparation method of the composite material, the heating temperature is 60-80 ℃; the stirring and mixing conditions are that stirring is carried out for 3-8min at the rotating speed of 300-400 r/min; the reaction condition is that the reaction is carried out for 2min at 70-80 ℃; the condition of the continuous reaction is that the reaction is carried out for 3min at 70-80 ℃; the heating temperature is raised to 100-105 ℃ at a heating speed of 5-10 ℃/min; the curing condition is curing for 4-6 hours at 95-100 ℃.
5. A creep resistant composite according to claim 1, wherein: in the preparation method of the composite material, the molecular weight of the polytetrahydrofuran ether glycol is 1000; the mass ratio of the polytetrahydrofuran ether glycol, the modified castor oil, the 1, 4-butanediol, the 4,4' -diphenylmethane diisocyanate, the modified silicon dioxide, the modified cellulose fiber and other auxiliary agents is 80-100:10-15:12-22:66.5-90.0:4-9:3-8:2.5-3.0; the other auxiliary agent is formed by mixing titanium dioxide and tartaric acid; the mass ratio of the titanium dioxide to the tartaric acid is 1.0-2.0:3.5.
6. A creep resistant composite according to claim 1, wherein: in the step 1), the mass ratio of the oleic acid to the 3-mercaptopropyl triethoxysilane to the photoinitiator is 28-30:20-22.5:1.1 to 1.6; the ultraviolet irradiation treatment is carried out under 365nm and 1400mW for 20-25h.
7. A creep resistant composite according to claim 1, wherein: in the step 2), the stirring and mixing conditions are that stirring and mixing are carried out for 5-10min under 200-300 r/min; the pH value is adjusted to 8.5-9.0; the condition of ultrasonic treatment is that the ultrasonic treatment is carried out for 30-45min under 600-650W; the heating and stirring conditions are that stirring is carried out for 10-15 hours at the temperature of 58.5-60 ℃ and the rotating speed of 300-450 r/min; the primary drying condition is that drying is carried out at 80 ℃; the washing is carried out for 3 times by adopting alcohol washing; the secondary drying is freeze drying.
8. A creep resistant composite according to claim 1, wherein: in the step 2), the dosage ratio of the absolute ethyl alcohol, the deionized water, the silicon dioxide and the modified coupling agent is 100-110mL:1mL:5.0-5.5g:4.5g.
9. Use of a creep-resistant composite according to any one of claims 1-8, wherein the composite is applied in a dental mouthpiece.
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