CN106349508A - Vulcanizing compounding agent micro capsule suspension, and preparation method and application thereof - Google Patents
Vulcanizing compounding agent micro capsule suspension, and preparation method and application thereof Download PDFInfo
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- CN106349508A CN106349508A CN201610855040.3A CN201610855040A CN106349508A CN 106349508 A CN106349508 A CN 106349508A CN 201610855040 A CN201610855040 A CN 201610855040A CN 106349508 A CN106349508 A CN 106349508A
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- 239000003094 microcapsule Substances 0.000 title claims abstract description 104
- 239000000725 suspension Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 title abstract description 126
- 238000013329 compounding Methods 0.000 title abstract description 118
- 239000012188 paraffin wax Substances 0.000 claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000463 material Substances 0.000 claims abstract description 30
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 24
- 239000012071 phase Substances 0.000 claims description 37
- 239000003921 oil Substances 0.000 claims description 22
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 13
- 239000011593 sulfur Substances 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 235000021355 Stearic acid Nutrition 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 10
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 10
- 239000008117 stearic acid Substances 0.000 claims description 10
- 239000011787 zinc oxide Substances 0.000 claims description 9
- 239000008346 aqueous phase Substances 0.000 claims description 7
- 229940096992 potassium oleate Drugs 0.000 claims description 6
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 claims description 6
- 239000004166 Lanolin Chemical class 0.000 claims description 5
- 229940039717 lanolin Drugs 0.000 claims description 5
- 235000019388 lanolin Nutrition 0.000 claims description 5
- 239000012744 reinforcing agent Substances 0.000 claims description 5
- -1 sorbitan fatty acid ester Chemical class 0.000 claims description 5
- 229920000136 polysorbate Polymers 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- 229950008882 polysorbate Drugs 0.000 claims description 3
- 229920002545 silicone oil Polymers 0.000 claims description 3
- 235000010446 mineral oil Nutrition 0.000 claims description 2
- 238000005987 sulfurization reaction Methods 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims 18
- 239000002253 acid Substances 0.000 claims 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims 1
- 238000004073 vulcanization Methods 0.000 abstract description 147
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 abstract description 66
- 239000007787 solid Substances 0.000 abstract description 47
- 239000002775 capsule Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 10
- 230000007423 decrease Effects 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 62
- 229920006173 natural rubber latex Polymers 0.000 description 43
- 239000002245 particle Substances 0.000 description 14
- 229920001971 elastomer Polymers 0.000 description 11
- 244000043261 Hevea brasiliensis Species 0.000 description 9
- 229920003052 natural elastomer Polymers 0.000 description 9
- 229920001194 natural rubber Polymers 0.000 description 9
- 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 7
- 238000002156 mixing Methods 0.000 description 7
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 7
- 229920000053 polysorbate 80 Polymers 0.000 description 7
- 230000003712 anti-aging effect Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- ICLYJLBTOGPLMC-KVVVOXFISA-N (z)-octadec-9-enoate;tris(2-hydroxyethyl)azanium Chemical compound OCCN(CCO)CCO.CCCCCCCC\C=C/CCCCCCCC(O)=O ICLYJLBTOGPLMC-KVVVOXFISA-N 0.000 description 4
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000005357 flat glass Substances 0.000 description 4
- 238000009864 tensile test Methods 0.000 description 4
- 229940117013 triethanolamine oleate Drugs 0.000 description 4
- 239000004636 vulcanized rubber Substances 0.000 description 4
- 230000002411 adverse Effects 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- 229960004274 stearic acid Drugs 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229940070765 laurate Drugs 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- 229920002396 Polyurea Polymers 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 239000004548 suspo-emulsion Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000012360 testing method Methods 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
-
- 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
- C08K3/02—Elements
- C08K3/06—Sulfur
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
- C08L7/02—Latex
-
- 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
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
本发明提供了一种硫化配合剂微胶囊悬浮液，包括25wt％～48wt％硫化配合剂微胶囊、1wt％～5wt％乳化剂和48wt％～70wt％水；其中，所述硫化配合剂微胶囊包括作为壁材的固体石蜡和作为囊芯的硫化配合剂，所述固体石蜡占所述硫化配合剂微胶囊质量的百分含量为30％～65％。将本发明提供的硫化配合剂微胶囊悬浮液应用于天然胶乳硫化中，实现了天然胶乳硫化配合剂根据实际需要的温度进行可控释放，能够有效避免天然胶乳配合过程中某些硫化配合剂影响天然胶乳稳定性，从而导致其质量下降的问题。此外，本发明提供了所述硫化配合剂微胶囊悬浮液的制备方法，操作简单，条件易控，硫化配合剂微胶囊包覆率高。The invention provides a vulcanization compounding agent microcapsule suspension, comprising 25wt%-48wt% vulcanization compounding agent microcapsules, 1wt%-5wt% emulsifier and 48wt%-70wt% water; wherein, the vulcanization compounding agent microcapsules It includes solid paraffin as a wall material and vulcanization compounding agent as a capsule core, and the percentage content of the solid paraffin in the mass of the vulcanization compounding agent microcapsule is 30% to 65%. Applying the vulcanization compounding agent microcapsule suspension provided by the present invention to the vulcanization of natural latex realizes the controllable release of the natural latex vulcanization compounding agent according to the actual temperature, and can effectively avoid the influence of certain vulcanization compounding agents in the natural latex compounding process The stability of natural latex, which leads to the problem of its quality decline. In addition, the invention provides a preparation method of the microcapsule suspension of the vulcanization compounding agent, which is simple in operation, easy to control the conditions, and has a high coating rate of the microcapsules of the vulcanization compounding agent.
Description
技术领域technical field
本发明涉及天然胶乳硫化技术领域，特别涉及一种硫化配合剂微胶囊悬浮液及其制备方法和应用。The invention relates to the technical field of natural rubber latex vulcanization, in particular to a vulcanization compounding agent microcapsule suspension and its preparation method and application.
背景技术Background technique
微胶囊是由天然或合成高分子制成的微型容器，由被包囊材料(称为囊芯)和包囊材料(称为壁材)组成，是将固体、液体或气体包裹在一个微小的胶囊中。形成微胶囊的物质与外界环境相隔离，可以免受环境的影响，从而保持其稳定性；当在一定条件下，被包封物质又可以释放出来，而不影响其发挥相应的作用。Microcapsules are micro-containers made of natural or synthetic polymers, consisting of encapsulated materials (called capsule cores) and encapsulated materials (called wall materials), which enclose solids, liquids or gases in a tiny in capsules. The substances forming microcapsules are isolated from the external environment and can be protected from the influence of the environment, thereby maintaining their stability; under certain conditions, the encapsulated substances can be released without affecting their corresponding functions.
对橡胶进行硫化能够有效改善橡胶的物理或化学性能。为了能够减少硫化剂或根据实际需要而添加的各种助剂对橡胶性能产生的不利影响，保证硫化效果，提高橡胶产品的性能，研究者们研制出可用作橡胶硫化剂的硫磺微胶囊或硫化助剂微胶囊，具体是以硫磺或硫化助剂为囊芯，以脲醛树脂或聚脲树脂等聚合物为壁材，以期在一定温度下使包囊材料熔化然后释放出硫化剂或助剂。Vulcanization of rubber can effectively improve the physical or chemical properties of rubber. In order to reduce the adverse effects of vulcanizing agents or various additives added according to actual needs on rubber properties, ensure the vulcanization effect, and improve the performance of rubber products, researchers have developed sulfur microcapsules or vulcanizing agents that can be used as rubber vulcanizing agents. Vulcanization aid microcapsules, specifically, use sulfur or vulcanization aids as the capsule core, and polymers such as urea-formaldehyde resin or polyurea resin as the wall material, in order to melt the encapsulation material at a certain temperature and then release the vulcanization agent or auxiliary agent .
但是该硫磺微胶囊或硫化助剂微胶囊只能用于天然橡胶固体颗粒生胶的高温硫化；由于高温会破坏天然胶乳的稳定性，故上述硫磺微胶囊或硫化助剂微胶囊并不能用于天然胶乳的低温硫化。But this sulfur microcapsule or vulcanization aid microcapsule can only be used for the high-temperature vulcanization of natural rubber solid particle raw rubber; Because high temperature can destroy the stability of natural latex, so above-mentioned sulfur microcapsule or vulcanization aid microcapsule can not be used for Low temperature vulcanization of natural latex.
发明内容Contents of the invention
本发明的目的在于提供一种硫化配合剂微胶囊悬浮液及其制备方法和应用，将本发明提供的硫化配合剂微胶囊悬浮液应用于天然胶乳硫化中，能够实现天然胶乳硫化配合剂根据实际需要的温度进行可控释放，有效避免天然胶乳配合过程中某些硫化配合剂影响天然胶乳稳定性，从而导致其质量下降的问题。The purpose of the present invention is to provide a kind of vulcanization compounding agent microcapsule suspension and its preparation method and application, apply the vulcanization compounding agent microcapsule suspension provided by the present invention in natural rubber latex vulcanization, can realize natural latex vulcanization compounding agent according to actual conditions Controlled release at the required temperature can effectively avoid the problem that certain vulcanization compounding agents affect the stability of natural latex during the compounding process of natural latex, resulting in a decline in its quality.
本发明提供了一种硫化配合剂微胶囊悬浮液，包括以下组分：The invention provides a microcapsule suspension of vulcanization compounding agent, comprising the following components:
25wt％～48wt％硫化配合剂微胶囊；25wt% ~ 48wt% vulcanization compounding agent microcapsules;
1wt％～5wt％乳化剂；1wt%～5wt% emulsifier;
48wt％～70wt％水；48wt%～70wt% water;
其中，所述硫化配合剂微胶囊包括作为壁材的固体石蜡和作为囊芯的硫化配合剂，所述固体石蜡占所述硫化配合剂微胶囊质量的百分含量为30％～65％。Wherein, the vulcanization compounding agent microcapsules include solid paraffin as a wall material and vulcanization compounding agent as a capsule core, and the percentage of the solid paraffin in the mass of the vulcanization compounding agent microcapsules is 30% to 65%.
优选的，所述硫化配合剂微胶囊悬浮液包括以下组分：Preferably, the vulcanization compounding agent microcapsule suspension comprises the following components:
32wt％～40wt％硫化配合剂微胶囊；32wt% ~ 40wt% vulcanization compounding agent microcapsules;
2wt％～4wt％乳化剂；2wt%～4wt% emulsifier;
56wt％～64wt％水。56wt% ~ 64wt% water.
优选的，所述固体石蜡占所述硫化配合剂微胶囊质量的百分含量为40％～55％。Preferably, the solid paraffin wax accounts for 40%-55% of the mass of the vulcanization compounding agent microcapsules.
优选的，所述固体石蜡的熔点为50～70℃。Preferably, the melting point of the solid paraffin is 50-70°C.
优选的，所述硫化配合剂包括硫磺、氧化锌、促进剂、防老剂和补强剂中的一种或多种。Preferably, the vulcanization compounding agent includes one or more of sulfur, zinc oxide, accelerator, anti-aging agent and reinforcing agent.
优选的，所述乳化剂包括聚山梨酯、失水山梨醇脂肪酸酯、月桂酸盐、硬脂酸、羊毛脂衍生物、脂肪醇聚氧乙烯醚、油酸三乙醇胺、油酸钾、硅油和芳烃矿物油中的一种或多种。Preferably, the emulsifier includes polysorbate, sorbitan fatty acid ester, laurate, stearic acid, lanolin derivatives, fatty alcohol polyoxyethylene ether, triethanolamine oleate, potassium oleate, silicone oil and one or more of aromatic mineral oils.
本发明提供了上述技术方案所述硫化配合剂微胶囊悬浮液的制备方法，包括以下步骤：The present invention provides the preparation method of vulcanization complexing agent microcapsule suspension described in above-mentioned technical scheme, comprises the following steps:
(1)将硫化配合剂与熔融的固体石蜡混合，得到油相；将乳化剂与水混合，得到水相；(1) mixing the vulcanization compounding agent with molten solid paraffin to obtain an oil phase; mixing the emulsifier with water to obtain a water phase;
(2)将所述步骤(1)中油相加入到水相中，得到硫化配合剂微胶囊悬浮液。(2) adding the oil phase in the step (1) into the water phase to obtain a vulcanization compounding agent microcapsule suspension.
优选的，步骤(1)所述水的温度为80～95℃。Preferably, the temperature of the water in step (1) is 80-95°C.
优选的，步骤(2)所述加入的方式为滴加。Preferably, the adding method described in step (2) is dropwise addition.
本发明提供了上述技术方案所述硫化配合剂微胶囊悬浮液或上述技术方案所述制备方法制备得到的硫化配合剂微胶囊悬浮液在天然胶乳硫化中的应用。The present invention provides the application of the vulcanization compounding agent microcapsule suspension in the above technical solution or the vulcanization compounding agent microcapsule suspension prepared by the preparation method in the above technical solution in the vulcanization of natural rubber latex.
本发明提供了一种硫化配合剂微胶囊悬浮液，包括25wt％～48wt％硫化配合剂微胶囊、1wt％～5wt％乳化剂和48wt％～70wt％水；其中，所述硫化配合剂微胶囊包括作为壁材的固体石蜡和作为囊芯的硫化配合剂，所述固体石蜡占所述硫化配合剂微胶囊质量的百分含量为30％～65％。本发明将硫化配合剂包覆在固体石蜡壁材中，得到的硫化配合剂微胶囊能够在乳化剂和水组成的水相中形成稳定均一的悬浮乳液，能够避免硫化配合剂微胶囊在贮存过程中发生沉降、聚结的现象，保持硫化配合剂微胶囊原有的分散程度。将本发明提供的硫化配合剂微胶囊悬浮液应用于天然胶乳硫化中，能够有效避免所述硫化配合剂与天然胶乳粒子直接接触，造成天然胶乳稳定性下降的问题；当硫化温度达到或超过固体石蜡壁材熔点时，硫化配合剂能够破壁释放出来，与天然胶乳粒子发生交联反应，实现天然胶乳的硫化，且所添加的固体石蜡壁材对硫化的天然胶乳的力学性能并无不良影响。The invention provides a vulcanization compounding agent microcapsule suspension, comprising 25wt%-48wt% vulcanization compounding agent microcapsules, 1wt%-5wt% emulsifier and 48wt%-70wt% water; wherein, the vulcanization compounding agent microcapsules It includes solid paraffin as a wall material and vulcanization compounding agent as a capsule core, and the percentage content of the solid paraffin in the mass of the vulcanization compounding agent microcapsule is 30% to 65%. In the present invention, the vulcanization compounding agent is coated in the solid paraffin wall material, and the obtained vulcanization compounding agent microcapsules can form a stable and uniform suspoemulsion in the water phase composed of emulsifier and water, which can prevent the vulcanization compounding agent microcapsules from being stored during storage. Settling and agglomeration occur in the medium, and the original dispersion degree of the microcapsules of the vulcanization compounding agent is maintained. Applying the vulcanization compounding agent microcapsule suspension provided by the invention to the vulcanization of natural latex can effectively avoid the direct contact between the vulcanization compounding agent and the natural latex particles, causing the problem that the stability of the natural latex decreases; when the vulcanization temperature reaches or exceeds the solid At the melting point of the paraffin wall material, the vulcanization compounding agent can break through the wall and release, and have a cross-linking reaction with the natural latex particles to realize the vulcanization of the natural latex, and the added solid paraffin wall material has no adverse effect on the mechanical properties of the vulcanized natural latex .
此外，本发明提供了所述硫化配合剂微胶囊悬浮液的制备方法，将硫化配合剂与熔融的固体石蜡混合，得到油相；将乳化剂与水混合，得到水相；将所述油相加入到水相中，得到硫化配合剂微胶囊悬浮液。本发明提供的硫化配合剂微胶囊悬浮液的制备方法，操作简单，条件易控，硫化配合剂微胶囊包覆率高，可达80％以上。In addition, the present invention provides a preparation method of the vulcanization compounding agent microcapsule suspension, mixing the vulcanization compounding agent with molten solid paraffin to obtain an oil phase; mixing an emulsifier with water to obtain a water phase; Add it into the water phase to obtain the vulcanization compounding agent microcapsule suspension. The preparation method of the microcapsule suspension of the vulcanization compounding agent provided by the invention has the advantages of simple operation, easy control of the conditions, and a high coating rate of the microcapsules of the vulcanization compounding agent, which can reach more than 80%.
具体实施方式detailed description
本发明提供了一种硫化配合剂微胶囊悬浮液，包括以下组分：The invention provides a microcapsule suspension of vulcanization compounding agent, comprising the following components:
25wt％～48wt％硫化配合剂微胶囊；25wt% ~ 48wt% vulcanization compounding agent microcapsules;
1wt％～5wt％乳化剂；1wt%～5wt% emulsifier;
48wt％～70wt％水；48wt%～70wt% water;
其中，所述硫化配合剂微胶囊包括作为壁材的固体石蜡和作为囊芯的硫化配合剂，所述固体石蜡占所述硫化配合剂微胶囊质量的百分含量为30％～65％。Wherein, the vulcanization compounding agent microcapsules include solid paraffin as a wall material and vulcanization compounding agent as a capsule core, and the percentage of the solid paraffin in the mass of the vulcanization compounding agent microcapsules is 30% to 65%.
本发明提供的硫化配合剂微胶囊悬浮液包括25wt％～48wt％的硫化配合剂微胶囊，优选为30wt％～45wt％，更优选为32wt％～40wt％。在本发明中，所述硫化配合剂微胶囊的粒度优选为80～150μm，更优选为95～130μm，最优选为105～115μm。The vulcanization compounding agent microcapsule suspension provided by the present invention comprises 25wt%-48wt% vulcanization compounding agent microcapsules, preferably 30wt%-45wt%, more preferably 32wt%-40wt%. In the present invention, the particle size of the vulcanization compounding agent microcapsules is preferably 80-150 μm, more preferably 95-130 μm, most preferably 105-115 μm.
在本发明中，所述硫化配合剂微胶囊包括作为壁材的固体石蜡和作为囊芯的硫化配合剂，所述固体石蜡占所述硫化配合剂微胶囊质量的百分含量优选为30％～65％，更优选为40％～55％，最优选为45％～50％；余量为囊芯。In the present invention, the vulcanization compounding agent microcapsules include solid paraffin as the wall material and the vulcanization compounding agent as the capsule core, and the percentage of the solid paraffin in the mass of the vulcanization compounding agent microcapsules is preferably 30% to 30%. 65%, more preferably 40%-55%, most preferably 45%-50%; the balance is the capsule core.
在本发明中，所述固体石蜡的熔点优选为50～70℃，更优选为55～65℃。在本发明中，天然胶乳硫化的温度为50～70℃，温度太低则硫化时间长而生产效率低，温度太高导致天然胶乳稳定性下降，容易产生凝块，对生产工艺和产品质量造成不良影响。本发明对于所述固体石蜡的种类或来源没有特殊的限定，采用本领域技术人员熟知的固体石蜡即可。本发明优选采用粗石蜡、半精炼石蜡或全精炼石蜡。In the present invention, the melting point of the solid paraffin is preferably 50-70°C, more preferably 55-65°C. In the present invention, the temperature of natural rubber latex vulcanization is 50～70 ℃, and if temperature is too low, then vulcanization time is long and production efficiency is low, and temperature is too high and causes natural latex stability to decline, easily produces clot, and production process and product quality are caused. adverse effects. The present invention has no special limitation on the type or source of the paraffin wax, and the paraffin wax well known to those skilled in the art can be used. The present invention preferably adopts crude paraffin, semi-refined paraffin or fully refined paraffin.
在本发明中，所述硫化配合剂的粒度优选为50～100μm，更优选为70～90μm。本发明对于所述硫化配合剂的种类没有特殊的限定，采用本领域技术人员熟知的用于天然胶乳硫化的硫化配合剂即可。在本发明中，所述硫化配合剂优选包括硫磺、氧化锌、促进剂、防老剂和补强剂中的一种或多种。本发明对于所述促进剂、防老剂和补强剂的种类没有特殊的限定，采用本领域技术人员熟知的促进剂、防老剂和补强剂即可。在实际应用中，可根据对于硫化天然胶乳性能的具体需要，选择硫化配合剂的添加种类、每种硫化配合剂的具体型号以及每种硫化配合剂的添加量。In the present invention, the particle size of the vulcanization compounding agent is preferably 50-100 μm, more preferably 70-90 μm. In the present invention, there is no special limitation on the type of the vulcanization compounding agent, and the vulcanization compounding agent for natural rubber latex vulcanization well known to those skilled in the art can be used. In the present invention, the vulcanization compounding agent preferably includes one or more of sulfur, zinc oxide, accelerator, anti-aging agent and reinforcing agent. In the present invention, there is no special limitation on the types of the accelerator, anti-aging agent and reinforcing agent, and accelerators, anti-aging agents and reinforcing agents well known to those skilled in the art can be used. In practical applications, the type of vulcanization compounding agent, the specific model of each vulcanization compounding agent and the amount of each vulcanization compounding agent can be selected according to the specific needs of the performance of vulcanized natural rubber latex.
在本发明中，所述硫化配合剂微胶囊中囊芯的粒度优选为50～100μm，更优选为65～85μm；所述硫化配合剂微胶囊中壁材的厚度优选为50～70μm，更优选为55～65μm。In the present invention, the particle size of the capsule core in the vulcanization compounding agent microcapsule is preferably 50-100 μm, more preferably 65-85 μm; the thickness of the wall material in the vulcanization compounding agent microcapsule is preferably 50-70 μm, more preferably It is 55-65 μm.
本发明提供的硫化配合剂微胶囊悬浮液包括1wt％～5wt％的乳化剂，优选为2wt％～4wt％。本发明对于所述乳化剂的种类没有特殊的限定，采用本领域技术人员熟知的乳化剂即可。在本发明中，所述乳化剂优选包括聚山梨酯(吐温)、失水山梨醇脂肪酸酯(司盘)、月桂酸盐、硬脂酸、羊毛脂衍生物、脂肪醇聚氧乙烯醚(平平加)、油酸三乙醇胺、油酸钾、硅油和芳烃矿物油中的一种或多种。在实际应用中，可根据对于硫化天然胶乳性能的具体需要，选择乳化剂的添加种类或者每类乳化剂的具体种类，以及每种乳化剂的添加量。在本发明的实施例中，所述乳化剂的组成具体可为：The vulcanization compounding agent microcapsule suspension provided by the invention includes 1wt%-5wt% emulsifier, preferably 2wt%-4wt%. In the present invention, there is no special limitation on the type of the emulsifier, and emulsifiers well known to those skilled in the art can be used. In the present invention, the emulsifier preferably includes polysorbate (Tween), sorbitan fatty acid ester (Span), laurate, stearic acid, lanolin derivatives, fatty alcohol polyoxyethylene ether One or more of (Pingpingjia), triethanolamine oleate, potassium oleate, silicone oil and aromatic mineral oil. In practical applications, the type of emulsifier added or the specific type of each type of emulsifier, and the amount of each emulsifier added can be selected according to the specific needs for the performance of vulcanized natural rubber latex. In an embodiment of the present invention, the composition of the emulsifier can specifically be:
司盘80、吐温80、平平加A-20、硬脂酸和十二烷基硫酸钠的质量比为6：2：1：1：1；The mass ratio of Span 80, Tween 80, Pingpinga A-20, stearic acid and sodium lauryl sulfate is 6:2:1:1:1;
或者可为司盘80、吐温80、羊毛脂、硬脂酸和油酸三乙醇胺的质量比为15：6：4：4：5；Alternatively, the mass ratio of Span 80, Tween 80, lanolin, stearic acid and triethanolamine oleate is 15:6:4:4:5;
或者可为司盘80、吐温80、平平加A-20、硬脂酸和油酸钾的质量比为16：5：4：3：2。Alternatively, the mass ratio of Span 80, Tween 80, Pingpinga A-20, stearic acid and potassium oleate is 16:5:4:3:2.
本发明提供的硫化配合剂微胶囊悬浮液包括48wt％～70wt％的水，优选为56wt％～64wt％。本发明对于所述水的种类没有特殊的限定，采用本领域技术人员熟知的水即可。The vulcanization compounding agent microcapsule suspension provided by the present invention includes 48wt%-70wt% of water, preferably 56wt%-64wt%. In the present invention, there is no special limitation on the type of water, and water well known to those skilled in the art can be used.
本发明提供了上述技术方案所述硫化配合剂微胶囊悬浮液的制备方法，包括以下步骤：The present invention provides the preparation method of vulcanization complexing agent microcapsule suspension described in above-mentioned technical scheme, comprises the following steps:
(1)将硫化配合剂与熔融的固体石蜡混合，得到油相；将乳化剂与水混合，得到水相；(1) mixing the vulcanization compounding agent with molten solid paraffin to obtain an oil phase; mixing the emulsifier with water to obtain a water phase;
(2)将所述步骤(1)中油相加入到水相中，得到硫化配合剂微胶囊悬浮液。(2) adding the oil phase in the step (1) into the water phase to obtain a vulcanization compounding agent microcapsule suspension.
本发明将硫化配合剂与熔融的固体石蜡混合，得到油相。本发明对于将所述固体石蜡熔融的方式没有特殊的限定，采用本领域技术人员熟知的熔融固体石蜡的方式即可。本发明优选将所述固体石蜡加热至80～95℃，搅拌，得到熔融的固体石蜡。本发明对于所述搅拌没有特殊的限定，采用本领域技术人员熟知的搅拌的技术方案即可。在本发明中，所述搅拌的速率优选为300～500rpm，更优选为350～450rpm；所述搅拌的时间优选为25～35min，更优选为28～32min。本发明对于将所述固体石蜡进行熔融所采用的装置没有特殊的限定，采用本领域技术人员熟知的装置即可。若在实验室中实施本发明提供的技术方案，优选将所述固体石蜡放入装有冷凝器的三口烧瓶或四口烧瓶中，加热进行熔融。In the invention, the vulcanization compounding agent is mixed with molten solid paraffin to obtain an oil phase. The method of melting the solid paraffin is not particularly limited in the present invention, and the method of melting the solid paraffin well known to those skilled in the art can be used. In the present invention, the solid paraffin is preferably heated to 80-95° C. and stirred to obtain molten solid paraffin. The present invention has no special limitation on the stirring, and a stirring technical solution well known to those skilled in the art can be used. In the present invention, the stirring speed is preferably 300-500 rpm, more preferably 350-450 rpm; the stirring time is preferably 25-35 min, more preferably 28-32 min. In the present invention, there is no special limitation on the device used for melting the solid paraffin, and a device well known to those skilled in the art can be used. If the technical scheme provided by the present invention is implemented in the laboratory, it is preferable to put the solid paraffin into a three-necked flask or a four-necked flask equipped with a condenser, and heat to melt.
将硫化配合剂与熔融的固体石蜡混合前，本发明优选将所述硫化配合剂进行研磨处理，使所述硫化配合剂的粒度为50～100μm。在本发明中，当所述硫化配合剂为多种配合剂的混合物时，将各种配合剂先混合再进行研磨处理，或者是将各种配合剂先分别进行研磨处理再混合均可。本发明对于所述研磨处理的方式没有特殊的限定，采用本领域技术人员熟知的能够将所述硫化配合剂的粒度研磨至符合要求的研磨处理方式即可，如砂子磨、球磨或胶体磨。在本发明的实施例中，具体是将所述硫化配合剂在球磨机中研磨72h。Before mixing the vulcanization compounding agent with the molten solid paraffin, the present invention preferably grinds the vulcanization compounding agent so that the particle size of the vulcanization compounding agent is 50-100 μm. In the present invention, when the vulcanization compounding agent is a mixture of various compounding agents, the various compounding agents are first mixed and then ground, or the various compounding agents are firstly ground separately and then mixed. The present invention has no special limitation on the grinding treatment method, and the grinding treatment method known to those skilled in the art that can grind the particle size of the vulcanization compound to meet the requirements can be used, such as sand mill, ball mill or colloid mill. In the embodiment of the present invention, specifically, the vulcanization compounding agent is ground in a ball mill for 72 hours.
本发明优选将硫化配合剂与熔融的固体石蜡混合后搅拌，得到油相。本发明对于所述搅拌没有特殊的限定，采用本领域技术人员熟知的搅拌的技术方案即可。在本发明中，所述搅拌的速率优选为800～1200rpm，更优选为900～1100rpm；所述搅拌的时间优选为0.5～2h，更优选为1～1.5h。In the present invention, the vulcanization compounding agent is preferably mixed with molten solid paraffin and then stirred to obtain an oil phase. The present invention has no special limitation on the stirring, and a stirring technical solution well known to those skilled in the art can be used. In the present invention, the stirring rate is preferably 800-1200 rpm, more preferably 900-1100 rpm; the stirring time is preferably 0.5-2 h, more preferably 1-1.5 h.
本发明将乳化剂与水混合，得到水相。在本发明中，所述水的温度优选为80～95℃，更优选为85～90℃。本发明优选将乳化剂与水混合后搅拌，得到水相。本发明对于所述搅拌没有特殊的限定，采用本领域技术人员熟知的搅拌的技术方案即可。在本发明中，所述搅拌的速率优选为300～500rpm，更优选为350～450rpm；所述搅拌的时间优选为25～35min，更优选为28～32min。In the present invention, the emulsifier is mixed with water to obtain an aqueous phase. In the present invention, the temperature of the water is preferably 80-95°C, more preferably 85-90°C. In the present invention, the emulsifier is preferably mixed with water and then stirred to obtain a water phase. The present invention has no special limitation on the stirring, and a stirring technical solution well known to those skilled in the art can be used. In the present invention, the stirring speed is preferably 300-500 rpm, more preferably 350-450 rpm; the stirring time is preferably 25-35 min, more preferably 28-32 min.
得到油相和水相后，本发明将所述油相加入到所述水相中，得到硫化配合剂微胶囊悬浮液。在本发明中，所述加入的方式优选为滴加，所述滴加的速率优选为50～80mL/min，更优选为60～70mL/min。本发明优选将所述油相加入到所述水相中后搅拌，得到硫化配合剂微胶囊悬浮液。本发明对于所述搅拌没有特殊的限定，采用本领域技术人员熟知的搅拌的技术方案即可。在本发明中，所述搅拌的速率优选为800～1200rpm，更优选为900～1100rpm；所述搅拌的时间优选为20～40min，更优选为25～35min。After the oil phase and the water phase are obtained, the present invention adds the oil phase into the water phase to obtain the vulcanization compounding agent microcapsule suspension. In the present invention, the adding method is preferably dropwise, and the dropping rate is preferably 50-80 mL/min, more preferably 60-70 mL/min. In the present invention, the oil phase is preferably added into the water phase and then stirred to obtain a microcapsule suspension of the vulcanization compounding agent. The present invention has no special limitation on the stirring, and a stirring technical solution well known to those skilled in the art can be used. In the present invention, the stirring rate is preferably 800-1200 rpm, more preferably 900-1100 rpm; the stirring time is preferably 20-40 min, more preferably 25-35 min.
将所述油相加入到所述水相中，搅拌结束后，本发明优选继续在搅拌条件下将所得到的物料冷却至室温，得到所述硫化配合剂微胶囊悬浮液。本发明优选采用冷水或冰块将所得到的物料快速冷却至室温，有利于保证所述硫化配合剂微胶囊悬浮液的稳定均一性。The oil phase is added to the water phase, and after the stirring is completed, the present invention preferably continues to cool the obtained material to room temperature under stirring conditions to obtain the microcapsule suspension of the vulcanization compounding agent. In the present invention, cold water or ice cubes are preferably used to rapidly cool the obtained material to room temperature, which is beneficial to ensure the stability and uniformity of the microcapsule suspension of the vulcanization compounding agent.
本发明提供了上述技术方案所述硫化配合剂微胶囊悬浮液或上述技术方案所述制备方法制备得到的硫化配合剂微胶囊悬浮液在天然胶乳硫化中的应用。本发明对于所述硫化配合剂微胶囊悬浮液在天然胶乳硫化中的应用方式没有特殊的限定，采用本领域技术人员熟知的天然胶乳硫化方式即可。The present invention provides the application of the vulcanization compounding agent microcapsule suspension in the above technical solution or the vulcanization compounding agent microcapsule suspension prepared by the preparation method in the above technical solution in the vulcanization of natural rubber latex. In the present invention, there is no special limitation on the application of the microcapsule suspension of the vulcanization compounding agent in the vulcanization of natural latex, and the natural latex vulcanization method well known to those skilled in the art can be used.
下面将结合本发明中的实施例，对本发明中的技术方案进行清楚、完整地描述。显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions in the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Apparently, the described embodiments are only some of the embodiments of the present invention, but not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
实施例1Example 1
(1)将23g硫磺、45g氧化锌、18g促进剂ZDC和14g防老剂BHT 264混合，放入球磨机中研磨72h，得到硫化配合剂；将100g熔点为64℃、牌号为64#固体石蜡放入装有冷凝器的三口烧瓶中，加热至85℃，在400rpm搅拌速率下搅拌30min，得到熔融的固体石蜡；(1) Mix 23g of sulfur, 45g of zinc oxide, 18g of accelerator ZDC and 14g of anti-aging agent BHT 264, put them into a ball mill and grind for 72 hours to obtain a vulcanization compounding agent; put 100g of solid paraffin wax with a melting point of 64°C and a grade of 64# into In a three-necked flask equipped with a condenser, heat to 85°C and stir for 30min at a stirring rate of 400rpm to obtain molten solid paraffin;
(2)将步骤(1)中硫化配合剂与熔融的固体石蜡混合，在1000rpm搅拌速率下搅拌1h，得到油相；将6g司盘80、2g吐温80、1g平平加A-20、1g硬脂酸和1g十二烷基硫酸钠加入到200g 85℃的水中，在400rpm搅拌速率下搅拌30min，得到水相；(2) Mix the vulcanization compounding agent in step (1) with molten solid paraffin, stir at a stirring rate of 1000rpm for 1 hour to obtain an oil phase; mix 6g Span 80, 2g Tween 80, 1g Pingpingjia A-20, 1g Stearic acid and 1g of sodium lauryl sulfate were added to 200g of water at 85°C, and stirred at a stirring rate of 400rpm for 30min to obtain an aqueous phase;
(3)将步骤(2)中油相以65mL/min的速率滴加到水相中，在1000rpm搅拌速率下搅拌30min，继续在搅拌条件下，采用冷水将得到的物料冷却至室温，得到硫化配合剂微胶囊悬浮液。(3) Add the oil phase in step (2) dropwise to the water phase at a rate of 65 mL/min, stir for 30 min at a stirring rate of 1000 rpm, and continue to cool the obtained material to room temperature with cold water under stirring conditions to obtain a vulcanized compound suspension of microcapsules.
将本发明实施例1制备的硫化配合剂微胶囊悬浮液用扫描电子显微镜观察，所述硫化配合剂微胶囊悬浮液中硫化配合剂微胶囊的粒度为80～150μm。The vulcanization compounding agent microcapsule suspension prepared in Example 1 of the present invention was observed with a scanning electron microscope, and the particle size of the vulcanization compounding agent microcapsules in the vulcanization compounding agent microcapsule suspension was 80-150 μm.
将16mL本发明实施例1制备的硫化配合剂微胶囊悬浮液加入到167g天然胶乳(所述天然胶乳中干胶的质量百分数为60％)中，在150rpm搅拌速率下搅拌1h，然后在室温下放置15天，得到配合天然胶乳，按照GB/T8289-2008规定对所述天然胶乳和配合天然胶乳的机械稳定性进行检测，按照GB/T14797.2-2008规定采用B型L2#转子对所述天然胶乳和配合天然胶乳的黏度进行检测，结果见表1。Add 16mL of the vulcanization compounding agent microcapsule suspension prepared in Example 1 of the present invention into 167g of natural latex (the mass percentage of dry rubber in the natural latex is 60%), stir for 1h at a stirring rate of 150rpm, and then Place it for 15 days to obtain the natural rubber latex. According to GB/T8289-2008, the mechanical stability of the natural rubber latex and the natural rubber latex is detected. According to the GB/T14797.2-2008, the B-type L2# rotor is used to test the The viscosity of natural latex and natural latex was tested, and the results are shown in Table 1.
由表1可知，将本发明实施例1制备的硫化配合剂微胶囊悬浮液与天然胶乳进行配合，得到的配合天然胶乳的机械稳定度略低于天然胶乳，但远高于国家标准GB/T8289-2008中天然胶乳的机械稳定度>650s的要求；同时，配合天然胶乳的黏度略高于天然胶乳，但能够满足实际需求。As can be seen from Table 1, the vulcanization compounding agent microcapsule suspension prepared in Example 1 of the present invention is compounded with natural latex, and the mechanical stability of the natural latex obtained is slightly lower than that of natural latex, but far higher than the national standard GB/T8289 -The requirement of mechanical stability of natural latex >650s in 2008; at the same time, the viscosity of blended natural latex is slightly higher than that of natural latex, but it can meet the actual demand.
将所述配合天然胶乳在65℃的水浴锅中硫化2h，保持150rpm的搅拌速率，保证配合天然胶乳内部传热均匀和防止表面结皮；硫化完成后，采用冷水冷却至室温，静置停放过夜，在平板玻璃上铺膜，室温下自然干燥成型，得到天然胶乳硫化胶膜。按照GB/T 528-2009规定裁剪哑铃状试样，在材料拉力试验机上以500mm/min的横梁移动速度测量所得的天然橡胶硫化胶膜的拉伸力学性能。测得所述天然橡胶硫化胶膜的拉伸强度为26.78MPa，拉断伸长率为756％，说明天然胶乳在此条件下实现了硫化交联，且所添加固体石蜡对其力学性能无不良影响。Vulcanize the compounded natural rubber latex in a water bath at 65°C for 2 hours, and maintain a stirring rate of 150rpm to ensure uniform heat transfer inside the compounded natural rubber latex and prevent skinning on the surface; , Lay a film on flat glass, and dry it naturally at room temperature to obtain a natural rubber latex vulcanized film. Cut dumbbell-shaped samples according to GB/T 528-2009, and measure the tensile mechanical properties of the obtained natural rubber vulcanized film on a material tensile testing machine at a beam moving speed of 500 mm/min. The measured tensile strength of the natural rubber vulcanized rubber film is 26.78MPa, and the elongation at break is 756%, indicating that the natural rubber latex has realized vulcanization and crosslinking under this condition, and the added solid paraffin is not harmful to its mechanical properties influences.
实施例2Example 2
(1)将23g硫磺、45g氧化锌、18g促进剂ZDC和14g防老剂BHT 264混合，放入球磨机中研磨72h，得到硫化配合剂；将100g熔点为60℃、牌号为60#固体石蜡放入装有冷凝器的三口烧瓶中，加热至80℃，在300rpm搅拌速率下搅拌35min，得到熔融的固体石蜡；(1) Mix 23g of sulfur, 45g of zinc oxide, 18g of accelerator ZDC and 14g of anti-aging agent BHT 264, put them into a ball mill and grind for 72 hours to obtain a vulcanization compound; put 100g of solid paraffin wax with a melting point of 60°C and a grade of 60# into In a three-necked flask equipped with a condenser, heat to 80°C and stir for 35min at a stirring rate of 300rpm to obtain molten solid paraffin;
(2)将步骤(1)中硫化配合剂与熔融的固体石蜡混合，在800rpm搅拌速率下搅拌2h，得到油相；将15g司盘80、6g吐温80、4g羊毛脂、4g硬脂酸和5g油酸三乙醇胺加入到800g80℃的水中，在500rpm搅拌速率下搅拌25min，得到水相；(2) Mix the vulcanization compounding agent in step (1) with molten solid paraffin, and stir for 2 hours at a stirring rate of 800rpm to obtain an oil phase; mix 15g of Span 80, 6g of Tween 80, 4g of lanolin, and 4g of stearic acid and 5g of triethanolamine oleate were added to 800g of water at 80°C, and stirred at a stirring rate of 500rpm for 25min to obtain an aqueous phase;
(3)将步骤(2)中油相以80mL/min的速率滴加到水相中，在800rpm搅拌速率下搅拌40min，继续在搅拌条件下，采用冷水将得到的物料冷却至室温，得到硫化配合剂微胶囊悬浮液。(3) Add the oil phase in step (2) dropwise to the water phase at a rate of 80 mL/min, stir for 40 min at a stirring rate of 800 rpm, and continue to cool the obtained material to room temperature with cold water under stirring conditions to obtain a vulcanized compound suspension of microcapsules.
将本发明实施例2制备的硫化配合剂微胶囊悬浮液用扫描电子显微镜观察，所述硫化配合剂微胶囊悬浮液中硫化配合剂微胶囊的粒度为80～150μm。The vulcanization compounding agent microcapsule suspension prepared in Example 2 of the present invention was observed with a scanning electron microscope, and the particle size of the vulcanization compounding agent microcapsules in the vulcanization compounding agent microcapsule suspension was 80-150 μm.
将45.6mL本发明实施例2制备的硫化配合剂微胶囊悬浮液加入到167g天然胶乳(所述天然胶乳中干胶的质量百分数为60％)中，在150rpm搅拌速率下搅拌1h，然后在室温下放置15天，得到配合天然胶乳，按照GB/T8289-2008规定对所述天然胶乳和配合天然胶乳的机械稳定性进行检测，按照GB/T14797.2-2008规定采用B型L2#转子对所述天然胶乳和配合天然胶乳的黏度进行检测，结果见表2。Add 45.6mL of the vulcanization compounding agent microcapsule suspension prepared in Example 2 of the present invention into 167g of natural latex (the mass percentage of dry rubber in the natural latex is 60%), stir for 1h at a stirring rate of 150rpm, and then stir at room temperature Place it under the ground for 15 days to obtain the natural rubber latex. According to the provisions of GB/T8289-2008, the mechanical stability of the natural latex and the natural latex is tested. According to the provisions of GB/T14797.2-2008, the B-type L2# The viscosity of the natural rubber latex and the combined natural rubber latex was tested, and the results are shown in Table 2.
由表2可知，将本发明实施例2制备的硫化配合剂微胶囊悬浮液与天然胶乳进行配合，得到的配合天然胶乳的机械稳定度略低于天然胶乳，但远高于国家标准GB/T8289-2008中天然胶乳的机械稳定度>650s的要求；同时，配合天然胶乳的黏度略高于天然胶乳，但能够满足实际需求。As can be seen from Table 2, the vulcanization compounding agent microcapsule suspension prepared in Example 2 of the present invention is compounded with natural latex, and the mechanical stability of the natural latex obtained is slightly lower than that of natural latex, but far higher than the national standard GB/T8289 -The requirement of mechanical stability of natural latex >650s in 2008; at the same time, the viscosity of blended natural latex is slightly higher than that of natural latex, but it can meet the actual demand.
将所述配合天然胶乳在65℃的水浴锅中硫化2h，保持150rpm的搅拌速率，保证配合天然胶乳内部传热均匀和防止表面结皮；硫化完成后，采用冷水冷却至室温，静置停放过夜，在平板玻璃上铺膜，室温下自然干燥成型，得到天然胶乳硫化胶膜。按照GB/T 528-2009规定裁剪哑铃状试样，在材料拉力试验机上以500mm/min的横梁移动速度测量所得的天然橡胶硫化胶膜的拉伸力学性能。测得所述天然橡胶硫化胶膜的拉伸强度为28.56MPa，拉断伸长率为793％，说明天然胶乳在此条件下实现了硫化交联，且所添加固体石蜡对其力学性能无不良影响。Vulcanize the compounded natural rubber latex in a water bath at 65°C for 2 hours, and maintain a stirring rate of 150rpm to ensure uniform heat transfer inside the compounded natural rubber latex and prevent skinning on the surface; , Lay a film on flat glass, and dry it naturally at room temperature to obtain a natural rubber latex vulcanized film. Cut dumbbell-shaped samples according to GB/T 528-2009, and measure the tensile mechanical properties of the obtained natural rubber vulcanized film on a material tensile testing machine at a beam moving speed of 500 mm/min. The measured tensile strength of the natural rubber vulcanized rubber film is 28.56MPa, and the elongation at break is 793%, indicating that the natural rubber latex has realized vulcanization and crosslinking under this condition, and the added solid paraffin is not harmful to its mechanical properties influences.
实施例3Example 3
(1)将120g硫磺放入球磨机中研磨72h，得到硫化配合剂；将200g熔点为64℃、牌号为64#固体石蜡放入装有冷凝器的三口烧瓶中，加热至95℃，在500rpm搅拌速率下搅拌25min，得到熔融的固体石蜡；(1) Put 120g of sulfur into a ball mill and grind for 72 hours to obtain a vulcanization compounding agent; put 200g of solid paraffin wax with a melting point of 64°C and a grade of 64# into a three-necked flask equipped with a condenser, heat to 95°C, and stir at 500rpm Stirring 25min under the speed, obtains the solid paraffin of melting;
(2)将步骤(1)中硫化配合剂与熔融的固体石蜡混合，在1200rpm搅拌速率下搅拌0.5h，得到油相；将16g司盘80、5g吐温80、4g平平加A-20、3g硬脂酸和2g油酸钾加入到500g95℃的水中，在300rpm搅拌速率下搅拌35min，得到水相；(2) Mix the vulcanization compounding agent in step (1) with molten solid paraffin, and stir for 0.5h at a stirring rate of 1200rpm to obtain an oil phase; mix 16g Span 80, 5g Tween 80, 4g Pingpingjia A-20, 3g of stearic acid and 2g of potassium oleate were added to 500g of water at 95°C, and stirred at a stirring rate of 300rpm for 35min to obtain an aqueous phase;
(3)将步骤(2)中油相以50mL/min的速率滴加到水相中，在1200rpm搅拌速率下搅拌20min，继续在搅拌条件下，采用冷水将得到的物料冷却至室温，得到硫化配合剂微胶囊悬浮液。(3) Add the oil phase in step (2) dropwise to the water phase at a rate of 50 mL/min, stir for 20 min at a stirring rate of 1200 rpm, and continue to cool the obtained material to room temperature with cold water under stirring conditions to obtain a vulcanized compound suspension of microcapsules.
将本发明实施例3制备的硫化配合剂微胶囊悬浮液用扫描电子显微镜观察，所述硫化配合剂微胶囊悬浮液中硫化配合剂微胶囊的粒度为80～150μm。The vulcanization compounding agent microcapsule suspension prepared in Example 3 of the present invention was observed with a scanning electron microscope, and the particle size of the vulcanization compounding agent microcapsules in the vulcanization compounding agent microcapsule suspension was 80-150 μm.
将10.5mL本发明实施例3制备的硫化配合剂微胶囊悬浮液加入到167g天然胶乳(所述天然胶乳中干胶的质量百分数为60％)中，在150rpm搅拌速率下搅拌1h，然后在室温下放置15天，得到配合天然胶乳，按照GB/T8289-2008规定对所述天然胶乳和配合天然胶乳的机械稳定性进行检测，按照GB/T14797.2-2008规定采用B型L2#转子对所述天然胶乳和配合天然胶乳的黏度进行检测，结果见表3。10.5 mL of vulcanization compounding agent microcapsule suspension prepared in Example 3 of the present invention was added to 167 g of natural rubber latex (the mass percentage of dry rubber in the natural latex was 60%), stirred for 1 h at a stirring rate of 150 rpm, and then stirred at room temperature Place it under the ground for 15 days to obtain the natural rubber latex. According to the provisions of GB/T8289-2008, the mechanical stability of the natural latex and the natural latex is tested. According to the provisions of GB/T14797.2-2008, the B-type L2# The viscosity of the natural rubber latex and the natural rubber latex mentioned above was tested, and the results are shown in Table 3.
由表3可知，将本发明实施例3制备的硫化配合剂微胶囊悬浮液与天然胶乳进行配合，得到的配合天然胶乳的机械稳定度略低于天然胶乳，但远高于国家标准GB/T8289-2008中天然胶乳的机械稳定度>650s的要求；同时，配合天然胶乳的黏度略高于天然胶乳，但能够满足实际需求。As can be seen from Table 3, the vulcanization compounding agent microcapsule suspension prepared in Example 3 of the present invention is compounded with natural latex, and the mechanical stability of the natural latex obtained is slightly lower than that of natural latex, but far higher than the national standard GB/T8289 -The requirement of mechanical stability of natural latex >650s in 2008; at the same time, the viscosity of blended natural latex is slightly higher than that of natural latex, but it can meet the actual demand.
在所述配合天然胶乳中加入研磨后的氧化锌、促进剂ZDC和防老剂MB，其中所述氧化锌、促进剂ZDC和防老剂MB与所述配合天然胶乳干胶的质量比为1：0.5：1：100；将所得物料在65℃的水浴锅中硫化2h，保持150rpm的搅拌速率，保证配合天然胶乳内部传热均匀和防止表面结皮；硫化完成后，采用冷水冷却至室温，静置停放过夜，在平板玻璃上铺膜，室温下自然干燥成型，得到天然胶乳硫化胶膜。按照GB/T 528-2009规定裁剪哑铃状试样，在材料拉力试验机上以500mm/min的横梁移动速度测量所得的天然橡胶硫化胶膜的拉伸力学性能。测得所述天然橡胶硫化胶膜的拉伸强度为30.54MPa，拉断伸长率为695％，说明天然胶乳在此条件下实现了硫化交联，且所添加固体石蜡对其力学性能无不良影响。Add ground zinc oxide, accelerator ZDC and antioxidant MB in the compounded natural latex, wherein the mass ratio of the zinc oxide, accelerator ZDC and antioxidant MB to the compounded natural latex dry rubber is 1:0.5 : 1:100; vulcanize the obtained material in a water bath at 65°C for 2 hours, and maintain a stirring rate of 150rpm to ensure uniform heat transfer inside the natural rubber latex and prevent skinning on the surface; after vulcanization is completed, cool to room temperature with cold water and let it stand Park overnight, spread film on flat glass, and dry naturally at room temperature to obtain natural rubber latex vulcanized film. Cut dumbbell-shaped samples according to GB/T 528-2009, and measure the tensile mechanical properties of the obtained natural rubber vulcanized film on a material tensile testing machine at a beam moving speed of 500 mm/min. The measured tensile strength of the natural rubber vulcanized rubber film is 30.54MPa, and the elongation at break is 695%, indicating that the natural rubber latex has realized vulcanization and crosslinking under this condition, and the added solid paraffin is not harmful to its mechanical properties influences.
实施例4Example 4
(1)将100g氧化锌、放入球磨机中研磨72h，得到硫化配合剂；将200g熔点为64℃、牌号为64#固体石蜡放入装有冷凝器的三口烧瓶中，加热至90℃，在500rpm搅拌速率下搅拌25min，得到熔融的固体石蜡；(1) Put 100g of zinc oxide into a ball mill and grind for 72 hours to obtain a vulcanization compounding agent; put 200g of solid paraffin wax with a melting point of 64°C and a grade of 64# into a three-necked flask equipped with a condenser, heat to 90°C, and Stir for 25min at a stirring rate of 500rpm to obtain molten paraffin wax;
(2)将步骤(1)中硫化配合剂与熔融的固体石蜡混合，在900rpm搅拌速率下搅拌1.5h，得到油相；将16g司盘80、5g吐温80、4g平平加A-20、3g硬脂酸和2g油酸钾加入到500g90℃的水中，在300rpm搅拌速率下搅拌35min，得到水相；(2) Mix the vulcanization compounding agent in step (1) with molten solid paraffin, and stir for 1.5 hours at a stirring rate of 900rpm to obtain an oil phase; mix 16g of Span 80, 5g of Tween 80, 4g of Pingpingjia A-20, 3g of stearic acid and 2g of potassium oleate were added to 500g of water at 90°C, and stirred at a stirring rate of 300rpm for 35min to obtain an aqueous phase;
(3)将步骤(2)中油相以70mL/min的速率滴加到水相中，在1200rpm搅拌速率下搅拌20min，继续在搅拌条件下，采用冷水将得到的物料冷却至室温，得到硫化配合剂微胶囊悬浮液。(3) Add the oil phase in step (2) dropwise to the water phase at a rate of 70 mL/min, stir for 20 min at a stirring rate of 1200 rpm, and continue to cool the obtained material to room temperature with cold water under stirring conditions to obtain a vulcanized compound suspension of microcapsules.
将本发明实施例4制备的硫化配合剂微胶囊悬浮液用扫描电子显微镜观察，所述硫化配合剂微胶囊悬浮液中硫化配合剂微胶囊的粒度为80～150μm。The vulcanization compounding agent microcapsule suspension prepared in Example 4 of the present invention was observed with a scanning electron microscope, and the particle size of the vulcanization compounding agent microcapsules in the vulcanization compounding agent microcapsule suspension was 80-150 μm.
将8mL本发明实施例4制备的硫化配合剂微胶囊悬浮液加入到167g天然胶乳(所述天然胶乳中干胶的质量百分数为60％)中，在150rpm搅拌速率下搅拌1h，在所得物料中加入研磨后的硫磺、促进剂ZDC和防老剂MB，其中所述氧化锌、促进剂ZDC和防老剂MB与所得物料中干胶的质量比为1.5：0.5：1：100；然后在室温下放置15天，得到配合天然胶乳，按照GB/T8289-2008规定对所述天然胶乳和配合天然胶乳的机械稳定性进行检测，按照GB/T14797.2-2008规定采用B型L2#转子对所述天然胶乳和配合天然胶乳的黏度进行检测，结果见表4。Add 8mL of the vulcanization complexing agent microcapsule suspension prepared in Example 4 of the present invention into 167g of natural rubber latex (the mass percentage of dry rubber in the natural latex is 60%), stir for 1h at a stirring rate of 150rpm, and in the obtained material Add the ground sulfur, accelerator ZDC and antioxidant MB, wherein the mass ratio of zinc oxide, accelerator ZDC and antioxidant MB to the dry glue in the obtained material is 1.5:0.5:1:100; then place it at room temperature After 15 days, the natural latex was obtained, and the mechanical stability of the natural latex and the natural latex was tested according to the provisions of GB/T8289-2008, and the natural latex was tested according to the provisions of GB/T14797. The viscosity of latex and natural latex was tested, and the results are shown in Table 4.
由表4可知，将本发明实施例4制备的硫化配合剂微胶囊悬浮液与天然胶乳进行配合，得到的配合天然胶乳的机械稳定度略低于天然胶乳，但远高于国家标准GB/T8289-2008中天然胶乳的机械稳定度>650s的要求；同时，配合天然胶乳的黏度略高于天然胶乳，但能够满足实际需求。As can be seen from Table 4, the vulcanization compounding agent microcapsule suspension prepared in Example 4 of the present invention is compounded with natural latex, and the mechanical stability of the natural latex obtained is slightly lower than that of natural latex, but far higher than the national standard GB/T8289 -The requirement of mechanical stability of natural latex >650s in 2008; at the same time, the viscosity of blended natural latex is slightly higher than that of natural latex, but it can meet the actual demand.
将所述配合天然胶乳在65℃的水浴锅中硫化2h，保持150rpm的搅拌速率，保证配合天然胶乳内部传热均匀和防止表面结皮；硫化完成后，采用冷水冷却至室温，静置停放过夜，在平板玻璃上铺膜，室温下自然干燥成型，得到天然胶乳硫化胶膜。按照GB/T 528-2009规定裁剪哑铃状试样，在材料拉力试验机上以500mm/min的横梁移动速度测量所得的天然橡胶硫化胶膜的拉伸力学性能。测得所述天然橡胶硫化胶膜的拉伸强度为26.12MPa，拉断伸长率为716％，说明天然胶乳在此条件下实现了硫化交联，且所添加固体石蜡对其力学性能无不良影响。Vulcanize the compounded natural rubber latex in a water bath at 65°C for 2 hours, and maintain a stirring rate of 150rpm to ensure uniform heat transfer inside the compounded natural rubber latex and prevent skinning on the surface; , Lay a film on flat glass, and dry it naturally at room temperature to obtain a natural rubber latex vulcanized film. Cut dumbbell-shaped samples according to GB/T 528-2009, and measure the tensile mechanical properties of the obtained natural rubber vulcanized film on a material tensile testing machine at a beam moving speed of 500 mm/min. The measured tensile strength of the natural rubber vulcanized rubber film is 26.12MPa, and the elongation at break is 716%, indicating that the natural rubber latex has realized vulcanization and crosslinking under this condition, and the added solid paraffin is not harmful to its mechanical properties influences.
由以上实施例可以看出，将本发明提供的硫化配合剂微胶囊悬浮液应用于天然胶乳硫化中，能够有效避免所述硫化配合剂与天然胶乳粒子直接接触，造成天然胶乳稳定性下降的问题；当硫化温度达到或超过固体石蜡壁材熔点时，硫化配合剂能够破壁释放出来，与天然胶乳粒子发生交联反应，实现天然胶乳的硫化，且所添加的固体石蜡壁材对硫化的天然胶乳的力学性能并无不良影响。As can be seen from the above examples, applying the vulcanization compounding agent microcapsule suspension provided by the present invention to the vulcanization of natural latex can effectively avoid the direct contact between the vulcanization compounding agent and the natural latex particles, causing the problem of decreased stability of the natural latex ; When the vulcanization temperature reaches or exceeds the melting point of the solid paraffin wall material, the vulcanization compounding agent can be released by breaking the wall, and cross-linking reaction occurs with the natural latex particles to realize the vulcanization of the natural latex, and the added solid paraffin wall material has a strong effect on the vulcanized natural rubber latex. The mechanical properties of the latex were not adversely affected.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.
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