CN114752232B - Elastomer-coated hollow glass bead and preparation method and application thereof - Google Patents
Elastomer-coated hollow glass bead and preparation method and application thereof Download PDFInfo
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- CN114752232B CN114752232B CN202210421332.1A CN202210421332A CN114752232B CN 114752232 B CN114752232 B CN 114752232B CN 202210421332 A CN202210421332 A CN 202210421332A CN 114752232 B CN114752232 B CN 114752232B
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- 239000011521 glass Substances 0.000 title claims abstract description 148
- 239000011324 bead Substances 0.000 title claims abstract description 137
- 229920001971 elastomer Polymers 0.000 title claims abstract description 58
- 239000000806 elastomer Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 claims abstract description 37
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims abstract description 35
- 238000005859 coupling reaction Methods 0.000 claims abstract description 27
- 239000004005 microsphere Substances 0.000 claims abstract description 25
- 230000033444 hydroxylation Effects 0.000 claims abstract description 20
- 238000005805 hydroxylation reaction Methods 0.000 claims abstract description 20
- 238000010168 coupling process Methods 0.000 claims abstract description 14
- 230000008878 coupling Effects 0.000 claims abstract description 12
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 30
- 239000005060 rubber Substances 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 22
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- 239000012670 alkaline solution Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 12
- 230000003712 anti-aging effect Effects 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- 239000007822 coupling agent Substances 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 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 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000011247 coating layer Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 230000001588 bifunctional effect Effects 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000001979 organolithium group Chemical group 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 14
- 239000011248 coating agent Substances 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000011325 microbead Substances 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/28—Glass
-
- 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
- C08K9/02—Ingredients treated with inorganic substances
-
- 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
- C08L21/00—Compositions of unspecified rubbers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The utility model provides a composite hollow glass bead, which comprises a hollow glass bead and an elastomer coated on the surface of the hollow glass bead; the elastomer includes a styrene-butadiene-styrene block copolymer. The utility model obtains the composite hollow glass microsphere with specific structure and composition. According to the preparation method, the surface hydroxylation treatment is carried out on the hollow glass beads, so that the surface activity of the hollow glass beads is stronger, and the hollow glass beads are introduced into the preparation method of SBS coupling functionalization, so that the effect of effectively coating the hollow glass beads is achieved. The production process provided by the utility model is simple and easy to control, and is beneficial to realizing industrial mass production and application.
Description
Technical Field
The utility model belongs to the technical field of rubber additive materials, relates to a composite hollow glass bead, a preparation method and application thereof, and in particular relates to an elastomer coated hollow glass bead, a preparation method and application thereof.
Background
The hollow glass bead has a true density of 0.1-1.0 g/cm 3 The inorganic spherical powder material with the particle size of 10-160 mu m and a hollow structure can be added into rubber to effectively reduce the density of the rubber, ensure the compressive strength and elasticity of the rubber and simultaneously produce light weightThe rubber can be widely applied to the fields of shoe materials and the like. However, the hollow glass beads are used as an inorganic material and have poor compatibility with rubber, so that the mechanical properties such as wear resistance, tensile bending strength and the like of the light rubber are obviously reduced.
In the research of other fields at present, there are also some modification technical schemes for hollow glass beads, for example, technical schemes for coating organic materials on the surfaces of hollow glass beads, and the coating materials mainly comprise the following materials: heat-sensitive composite resin, phenolic resin, polyurethane, nylon and other materials. For example, ma Zhi et al in the description of hollow glass beads coated with resin and a preparation method thereof, hollow glass beads are used as propping agents, heat-sensitive resin and corresponding curing agents are mixed and softened by heating, the hollow glass beads are added, stirred and filtered, and then the beads are heated and cured, so that the heat-sensitive resin is coated on the hollow glass beads. The method has the function of avoiding cracking when the slurry is solidified when the well cementation slurry is used in an oil field, thereby preventing the gas leakage phenomenon in the gas injection and oil jacking process. According to Mo Chuanyun et al, in the 'hollow glass bead coated with phenolic resin and preparation method thereof', the hollow glass bead is placed in a strong alkali solution to be stirred, so that the effect of surface hydroxylation is achieved, the bonding strength of a coating layer is improved, the hydroxylated hollow glass bead is mixed with a mixed aqueous solution of phenol and formaldehyde to be stirred at a controlled temperature, and the phenolic resin coated hollow bead is obtained after filtration, washing and drying. The hollow microsphere has the functions of providing certain toughness and wear resistance for the hollow microsphere and increasing the compressive strength of the hollow microsphere to a certain extent, thereby being more effectively applied to automobile weight-reducing materials, heat-insulating materials and coatings. For example, xia Xuelian et al propose a method for spraying a mixed solution of a polyhydroxy raw material and diisocyanate in a certain proportion on the surfaces of hollow glass beads, and carrying out in-situ polymerization reaction under a proper polymerization temperature condition. The method is mainly used for improving the overall toughness of the material after hollow microspheres are added in the process of casting nylon 6 castings. For example, lv Jiagu et al describe a method for coating nylon on the surface of hollow glass beads to reduce friction coefficient, improve surface smoothness and enhance corrosion resistance of the beads, which is mainly applied to road marking paint, building exterior wall coating and the like.
However, there are few reports on how to better apply the hollow glass beads to rubber additive materials, and it is difficult to directly apply the modified hollow glass beads in the studies in other fields.
Therefore, how to find a more suitable modified hollow glass bead, which can be better applied to rubber materials, should become one of the focuses of a great deal of first-line researchers in the field.
Disclosure of Invention
In view of the above, the technical problem to be solved by the utility model is to provide a composite hollow glass bead, a preparation method and application thereof, and in particular to an elastomer coated hollow glass bead. According to the preparation method, the surface hydroxylation treatment is carried out on the hollow glass beads, so that the surface activity of the hollow glass beads is stronger, and the hollow glass beads are introduced into the preparation method of SBS coupling functionalization, so that the effect of effectively coating the hollow glass beads is achieved. The production process provided by the utility model is simple and easy to control, and is beneficial to realizing industrial mass production and application.
The utility model provides a composite hollow glass bead, which comprises a hollow glass bead and an elastomer coated on the surface of the hollow glass bead;
the elastomer includes a styrene-butadiene-styrene block copolymer.
Preferably, the thickness of the elastomer coating layer is 0.05-0.3 μm;
the diameter of the composite hollow glass microsphere is 10-110 mu m;
the mass content of the elastomer in the composite hollow glass microsphere is 5% -30%;
and a chemical bond bonding structure is arranged between the elastomer and the surface of the hollow glass bead.
Preferably, the chemical bond bonding structure is specifically that the chemical bond bonding is realized through the surface hydroxyl functional groups of the hollow glass microspheres with the surface hydroxyl functional groups of the linear functionalized elastomer;
the linkage includes coupling;
the functionalization includes difunctional coupling functionalization;
the composite hollow glass beads comprise composite hollow glass beads for rubber products;
the rubber includes shoe rubber.
The utility model provides a preparation method of composite hollow glass beads, which comprises the following steps:
1) Mixing the hollow glass beads with an alkaline solution, and drying to obtain the hollow glass beads with surface hydroxylation;
2) Mixing the hollow glass beads subjected to surface hydroxylation treatment obtained in the steps with the linear functionalized styrene-butadiene-styrene block copolymer, and then performing cyclone dispersion and drying to obtain the composite hollow glass beads.
Preferably, the alkaline solution comprises sodium carbonate solution and/or sodium bicarbonate solution;
the mass concentration of the alkaline solution is 10% -30%;
the mass ratio of the hollow glass beads to the alkaline solution is (5-30): 100;
the temperature of the drying is 80-120 ℃;
the drying time is 3-5 h.
Preferably, the step 2) specifically includes:
premixing hydrocarbon solvent and styrene under the condition of nitrogen to obtain premix, adding an organic lithium initiator into the premix for polymerization reaction, adding butadiene for polymerization again, adding a bifunctional coupling agent for coupling reaction, adding an anti-aging agent after terminating the reaction, adding the hollow glass beads subjected to surface hydroxylation obtained in the steps for mixing, and finally performing cyclone dispersion and drying to obtain the composite hollow glass beads.
Preferably, the hydrocarbon solvent comprises cyclohexane;
the mass ratio of the hydrocarbon solvent to the styrene is (0.5-1.5): 1, a step of;
the temperature of the premixing is 40-80 ℃;
the organolithium initiator comprises n-butyllithium;
the mass ratio of the organic lithium initiator to the premix is (0.5-3): 100;
the temperature of the polymerization reaction is 40-80 ℃;
the polymerization reaction time is 10-60 min.
Preferably, the mass ratio of butadiene to styrene is (50-60): 100;
the temperature of the repolymerization is 40-80 ℃;
the time for the repolymerization is 10-50 min;
the difunctional coupling agent comprises epichlorohydrin;
the mass ratio of the difunctional coupling agent to the styrene is (5-20): 100;
the coupling reaction time is 10-30 min.
Preferably, the anti-aging agent comprises 2, 6-di-tert-butyl-p-cresol;
the mass ratio of the anti-aging agent to the reaction system after the coupling reaction is (0.5-3): 100;
the mass ratio of the hollow glass beads to the reaction system after the coupling reaction is (10-50): 100;
the mixing time is 10-30 min;
the mixing step further comprises a raffinate separation step;
the cyclone dispersing time is 10-30 min;
the drying temperature is 60-100 ℃.
The utility model also provides the application of the composite hollow glass bead prepared by any one of the technical schemes or the preparation method of any one of the technical schemes in the field of rubber product production.
The utility model provides a composite hollow glass bead, which comprises a hollow glass bead and an elastomer coated on the surface of the hollow glass bead; the elastomer includes a styrene-butadiene-styrene block copolymer. Compared with the prior art, the utility model researches the prior modified hollow glass beads, and considers that the prior art only mixes the high polymer material with the hollow glass beads before curing or before polymerization, so that the glass beads after curing or polymerization are not greatly changed in raw materials of the organic material, thus the binding force between the organic coating layer and the surfaces of the beads cannot be effectively improved, and the application of the modified hollow glass beads in the aspect of rubber additive materials is also defective. The utility model is based on research, particularly selects a thermoplastic elastomer, the material has high rubber elasticity at normal temperature, and can be softened when heated to a forming temperature, and the unique property is derived from the special molecular structure. Particularly, SBS, polystyrene chain segments (PS) in SBS molecules are aggregated into glassy hard segments which are uniformly distributed in a continuous phase formed by soft segments of Polybutadiene (PB), and at normal temperature, the PS chain segments play a role of physical crosslinking points to form a vulcanization-like network structure, and the material shows high elasticity of rubber; at high temperature, PS is thermally deformed and melted in an aggregated state, and the material is thermoplastic. And styrene-butadiene-styrene block copolymer (SBS) is a thermoplastic elastomer prepared by anionic polymerization of styrene and butadiene, and has excellent mechanical properties. The problem of neck blocking of the hollow glass bead in rubber can be effectively solved by coating a layer of SBS elastomer on the surface of the hollow glass bead. However, the surfaces of the hollow glass beads mainly contain substances such as silicon oxide, calcium oxide, sodium oxide and the like, and are relatively active, so that the hollow glass beads have certain polarity, so that the compatibility of the hollow glass beads and the hollow glass beads is poor, and the hollow glass beads are directly coated on the hollow glass beads on the premise of not changing the SBS structure, so that the problems of uneven coating, incapability of effective adhesion and the like are easily caused.
Based on the above, the utility model obtains the composite hollow glass microsphere with specific structure and composition. The SBS functionalized by the coupling method is particularly used for coating the hollow glass beads, so that the problems that the surface polarity of the beads can be reduced only by simply using a silane coupling agent to carry out surface treatment on the hollow glass beads and the binding force between the beads and a rubber contact surface cannot be effectively improved are effectively solved. According to the preparation method, the surface hydroxylation treatment is carried out on the hollow glass beads, so that the surface activity of the hollow glass beads is stronger, and the hollow glass beads are introduced into the preparation method of SBS coupling functionalization, so that the effect of effectively coating the hollow glass beads is achieved. The production process provided by the utility model is simple and easy to control, and is beneficial to realizing industrial mass production and application.
Drawings
FIG. 1 is a microscopic image of SBS coated hollow glass microspheres prepared according to the present utility model.
Detailed Description
For a further understanding of the present utility model, preferred embodiments of the utility model are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the utility model and are not limiting of the utility model claims.
All the raw materials of the present utility model are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art.
All raw materials of the present utility model are not particularly limited in purity, and the present utility model preferably employs industrial purity or purity requirements conventional in the field of rubber additive preparation.
All raw materials of the utility model, the brands and abbreviations of which belong to the conventional brands and abbreviations in the field of the related application are clear and definite, and the person skilled in the art can purchase from the market or prepare by the conventional method according to the brands, abbreviations and the corresponding application.
The utility model provides a composite hollow glass bead, which comprises a hollow glass bead and an elastomer coated on the surface of the hollow glass bead;
the elastomer includes a styrene-butadiene-styrene block copolymer.
In the present utility model, the diameter of the composite hollow glass microspheres is preferably 10 to 110. Mu.m, more preferably 30 to 80. Mu.m, still more preferably 50 to 60. Mu.m.
In the present utility model, the mass content of the elastomer in the composite hollow glass microsphere is preferably 5% to 30%, more preferably 10% to 25%, and still more preferably 15% to 20%.
In the present utility model, the thickness of the elastomer coating layer is preferably 0.05 to 0.3. Mu.m, more preferably 0.1 to 0.25. Mu.m, still more preferably 0.15 to 0.2. Mu.m.
In the utility model, the composite hollow glass microsphere preferably further comprises an anti-aging agent. Specifically, the elastomer preferably further comprises an anti-aging agent.
In the utility model, the elastomer and the surface of the hollow glass microsphere are preferably provided with chemical bond bonding structures.
In the present utility model, the chemical bond bonding structure is particularly preferably a chemical bond bonding structure realized by the surface hydroxyl functional group of the hollow glass microsphere surface hydroxylated and the functional group of the linear functionalized elastomer.
In the present utility model, the linkage preferably includes coupling.
In the present utility model, the functionalization preferably includes difunctional coupling functionalization.
In the present utility model, the composite hollow glass beads preferably include composite hollow glass beads for rubber products.
In the present utility model, the rubber preferably includes a shoe rubber.
The utility model provides a preparation method of composite hollow glass beads, which comprises the following steps:
1) Mixing the hollow glass beads with an alkaline solution, and drying to obtain the hollow glass beads with surface hydroxylation;
2) Mixing the hollow glass beads subjected to surface hydroxylation treatment obtained in the steps with the linear functionalized styrene-butadiene-styrene block copolymer, and then performing cyclone dispersion and drying to obtain the composite hollow glass beads.
According to the utility model, the hollow glass beads and the alkaline solution are mixed and dried to obtain the hollow glass beads with surface hydroxylation treatment.
In the present utility model, the alkaline solution preferably includes a sodium carbonate solution and/or a sodium bicarbonate solution, more preferably a sodium carbonate solution or a sodium bicarbonate solution.
In the present utility model, the mass concentration of the alkaline solution is preferably 10% to 30%, more preferably 14% to 26%, and still more preferably 18% to 22%.
In the utility model, the mass ratio of the hollow glass beads to the alkaline solution is preferably (5-30): 100, more preferably (10 to 25): 100, more preferably (15 to 20): 100.
in the present utility model, the temperature of the drying is preferably 80 to 120 ℃, more preferably 85 to 115 ℃, still more preferably 90 to 110 ℃, still more preferably 95 to 105 ℃.
In the present utility model, the drying time is preferably 3 to 5 hours, more preferably 3.4 to 4.6 hours, and still more preferably 3.8 to 4.2 hours.
The utility model mixes the hollow glass bead with the surface hydroxylation treatment and the linear functionalized styrene-butadiene-styrene segmented copolymer, and then obtains the composite hollow glass bead after cyclone dispersion and drying.
In the present utility model, the step 2) is specifically preferably:
premixing hydrocarbon solvent and styrene under the condition of nitrogen to obtain premix, adding an organic lithium initiator into the premix for polymerization reaction, adding butadiene for polymerization again, adding a bifunctional coupling agent for coupling reaction, adding an anti-aging agent after terminating the reaction, adding the hollow glass beads subjected to surface hydroxylation obtained in the steps for mixing, and finally performing cyclone dispersion and drying to obtain the composite hollow glass beads.
In the present utility model, the hydrocarbon solvent preferably includes cyclohexane.
In the present utility model, the mass ratio of the hydrocarbon solvent to the styrene is preferably (0.5 to 1.5): 1, more preferably (0.7 to 1.3): 1, more preferably (0.9 to 1.1): 1.
in the present utility model, the temperature of the premixing is preferably 40 to 80 ℃, more preferably 45 to 75 ℃, still more preferably 50 to 70 ℃, still more preferably 55 to 65 ℃.
In the present utility model, the organolithium initiator preferably includes n-butyllithium.
In the utility model, the mass ratio of the organic lithium initiator to the premix is preferably (0.5-3): 100, more preferably (1 to 2.5): 100, more preferably (1.5 to 2): 100.
in the present utility model, the polymerization reaction temperature is preferably 40 to 80 ℃, more preferably 45 to 75 ℃, still more preferably 50 to 70 ℃, still more preferably 55 to 65 ℃.
In the present utility model, the polymerization time is preferably 10 to 60 minutes, more preferably 20 to 50 minutes, and still more preferably 30 to 40 minutes.
In the present utility model, the mass ratio of butadiene to styrene is preferably (50 to 60): 100, more preferably (52 to 58): 100, more preferably (54 to 56): 100.
in the present utility model, the temperature of the repolymerization is preferably 40 to 80 ℃, more preferably 45 to 75 ℃, still more preferably 50 to 70 ℃, still more preferably 55 to 65 ℃.
In the present utility model, the time for the repolymerization is preferably 10 to 50 minutes, more preferably 15 to 45 minutes, still more preferably 20 to 40 minutes, still more preferably 25 to 35 minutes.
In the present utility model, the difunctional coupling agent preferably includes epichlorohydrin.
In the present utility model, the mass ratio of the bifunctional coupling agent to styrene is preferably (5 to 20): 100, more preferably (8 to 17): 100, more preferably (11 to 14): 100.
in the present utility model, the coupling reaction time is preferably 10 to 30 minutes, more preferably 14 to 26 minutes, and still more preferably 18 to 22 minutes.
In the present utility model, the antioxidant preferably includes 2, 6-di-t-butyl-p-cresol.
In the present utility model, the mass ratio of the antioxidant to the reaction system after the coupling reaction is preferably (0.5 to 3): 100, more preferably (1 to 2.5): 100, more preferably (1.5 to 2): 100.
in the utility model, the mass ratio of the hollow glass beads to the reaction system after the coupling reaction is preferably (10-50): 100, more preferably (15 to 45): 100, more preferably (20 to 40): 100, more preferably (25 to 35): 100.
in the present utility model, the mixing time is preferably 10 to 30 minutes, more preferably 14 to 26 minutes, and still more preferably 18 to 22 minutes.
In the present utility model, the mixing is preferably followed by a raffinate separation step.
In the present utility model, the cyclone dispersion time is preferably 10 to 30 minutes, more preferably 14 to 26 minutes, and still more preferably 18 to 22 minutes.
In the present utility model, the drying temperature is preferably 60 to 100 ℃, more preferably 65 to 95 ℃, still more preferably 70 to 90 ℃, still more preferably 75 to 85 ℃.
The utility model provides a better complete and refined integral preparation process, which ensures the structure and composition of the composite hollow glass bead and improves the performance of the composite hollow glass bead, and the preparation method of the elastomer coated hollow glass bead comprises the following steps:
surface hydroxylation treatment of hollow glass beads
(1) Adding the hollow glass beads into 10-30% weak alkaline solution such as sodium carbonate and sodium bicarbonate according to the mass ratio of 5-30%, stirring for 1h, and filtering;
(2) And (3) placing the filtered hollow glass microspheres in an oven, baking for 3-5 hours at 80-120 ℃, and screening by using a screen for standby.
Preparation of coupling functionalized SBS
The preparation process is as follows:
(1) Pressing cyclohexane and styrene into a polymerization kettle according to the mass ratio of 0.5-1.5 by using nitrogen, and heating to 40-80 ℃ under stirring;
(2) Adding 0.5-3% of n-butyl lithium, breaking impurities, rapidly initiating, and polymerizing for 10-60 min under stirring;
(3) Adding butadiene to continue the reaction for 10-50 min, and controlling the temperature to a set value (40-80 ℃);
(4) Adding 5-20% of epichlorohydrin for coupling reaction, stopping reaction by using ethanol after 10-30 min, and adding 0.5-3% of anti-aging agent 2, 6-di-tert-butyl-p-cresol;
(5) Adding 10-50% of hollow glass beads with surface hydroxylation treatment, and continuously stirring for 10-30 min after uniformly stirring;
separating the hollow glass beads from the residual liquid, dispersing the beads for 10-30 min by using normal-temperature cyclone, and drying the SBS coated beads by using hot air at 60-100 ℃ to obtain the SBS coated hollow glass beads.
The utility model provides the application of the composite hollow glass bead prepared by any one of the technical schemes or the preparation method of any one of the technical schemes in the field of rubber product production.
The utility model provides the hollow glass microsphere coated by the elastomer, and the preparation method and the application thereof. The utility model is a composite hollow glass bead with specific structure and composition, and the utility model adopts a coupling method functionalized SBS to coat the hollow glass bead, which effectively solves the problems that the surface polarity of the bead can be reduced only and the bonding force between the bead and the rubber contact surface can not be effectively improved by simply using a silane coupling agent to carry out surface treatment on the hollow glass bead. According to the preparation method, the surface hydroxylation treatment is carried out on the hollow glass beads, so that the surface activity of the hollow glass beads is stronger, and the hollow glass beads are introduced into the preparation method of SBS coupling functionalization, so that the effect of effectively coating the hollow glass beads is achieved. The production process provided by the utility model is simple and easy to control, and is beneficial to realizing industrial mass production and application.
For further explanation of the present utility model, the following details of a composite hollow glass bead, a preparation method and application thereof are provided in connection with examples, but it should be understood that these examples are implemented on the premise of the technical scheme of the present utility model, and detailed implementation and specific operation processes are given, which are only for further explanation of the features and advantages of the present utility model, but not for limitation of the claims of the present utility model, and the scope of protection of the present utility model is not limited to the following examples.
Examples 1 to 5
Surface hydroxylation treatment of hollow glass beads
(1) The true density is 0.38g/cm 3 Adding hollow glass beads with the particle diameter D50 of 30 mu m and the particle diameter D90 of 50 mu m into 10% of weak alkaline solution such as sodium carbonate and sodium bicarbonate according to the mass ratio of 10%, stirring for 1h, and filtering;
(2) And (3) placing the filtered hollow glass microspheres in an oven, baking at 120 ℃ for 5 hours, and screening by using a screen for standby.
Preparation of coupling functionalized SBS
The preparation process of the functionalized SBS by adopting the ZL201610121567.3 method is as follows:
(1) Pressing cyclohexane and styrene into a polymerization kettle according to the mass ratio of 1 by using nitrogen, and heating to 80 ℃ under stirring;
(2) Adding 1% of n-butyl lithium, breaking impurities, rapidly initiating, and polymerizing for 30min under stirring;
(3) Adding butadiene to continue the reaction for 30min, and controlling the temperature to be 80 ℃;
(4) Adding 5% of epichlorohydrin for coupling reaction, stopping the coupling reaction by using ethanol after 30min of reaction, and adding 0.5% of anti-aging agent 2, 6-di-tert-butyl-p-cresol;
(5) Adding 10%, 20%, 30%, 40% and 50% (examples 1-5) of hollow glass beads subjected to surface hydroxylation treatment, and continuing stirring for 10min after uniform stirring;
(6) Separating the hollow glass beads from the residual liquid, dispersing the beads for 30min by using normal-temperature cyclone, and drying the SBS coated beads by using hot air at 100 ℃ to obtain the SBS coated hollow glass beads.
And detecting the performance of the SBS coated hollow glass microsphere prepared by the embodiment of the utility model.
Referring to Table 1, table 1 shows the parameter index of the SBS coated hollow glass beads prepared by the present utility model.
TABLE 1
| Examples | Density g/cm 3 | D50\μm | D90\μm |
| 1 | 0.49 | 40 | 60 |
| 2 | 0.46 | 36 | 56 |
| 3 | 0.43 | 33 | 54.9 |
| 4 | 0.42 | 33 | 54 |
| 5 | 0.39 | 31.5 | 52 |
Referring to fig. 1, fig. 1 is a microscopic image of SBS coated hollow glass microspheres prepared according to the present utility model.
From the figure, it can be seen that most SBS can achieve a relatively uniform coating on the surface of the hollow glass microspheres, except for the small amount of SBS that occurs self-aggregation. The real density and the particle size distribution of the coated hollow micro beads are tested by using a real density tester and a laser particle sizer, so that the real density of the coated hollow micro beads is increased, the particle size is also increased, and the coating thickness of the SBS on the surfaces of the hollow glass micro beads is gradually reduced along with the increase of the adding mass ratio of the hollow glass micro beads.
The above detailed description of the elastomer-coated hollow glass microsphere, the preparation method and application thereof, which are provided herein, describes the principles and embodiments of the present utility model with specific examples, which are provided herein to assist in understanding the method and core concepts of the present utility model, including the best mode, and also to enable any person skilled in the art to practice the present utility model, including making and using any devices or systems, and performing any incorporated methods. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the utility model can be made without departing from the principles of the utility model and these modifications and adaptations are intended to be within the scope of the utility model as defined in the following claims. The scope of the patent protection is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.
Claims (9)
1. Application of composite hollow glass beads in rubber products;
the composite hollow glass bead comprises a hollow glass bead and an elastomer coated on the surface of the hollow glass bead;
the elastomer is a styrene-butadiene-styrene block copolymer;
a chemical bond bonding structure is arranged between the elastomer and the surface of the hollow glass bead;
the chemical bond bonding structure is specifically that chemical bond bonding is realized through the surface hydroxyl functional groups of the hollow glass beads with the surface hydroxylated and the functional groups of the linear functionalized elastomer;
the linkage includes coupling;
the functionalization includes difunctional coupling functionalization;
the thickness of the elastomer coating layer is 0.05-0.3 mu m;
the mass content of the elastomer in the composite hollow glass microsphere is 5-30%.
2. The use according to claim 1, wherein the composite hollow glass microspheres have a diameter of 10 to 110 μm.
3. The use according to claim 2, wherein the rubber comprises shoe rubber.
4. A method of preparing composite hollow glass microspheres in an application as claimed in any one of claims 1 to 3, comprising the steps of:
1) Mixing the hollow glass beads with an alkaline solution, and drying to obtain the hollow glass beads with surface hydroxylation;
2) Mixing the hollow glass beads subjected to surface hydroxylation treatment obtained in the steps with the linear functionalized styrene-butadiene-styrene block copolymer, and then performing cyclone dispersion and drying to obtain the composite hollow glass beads.
5. The preparation method according to claim 4, wherein the alkaline solution comprises sodium carbonate solution and/or sodium bicarbonate solution;
the mass concentration of the alkaline solution is 10% -30%;
the mass ratio of the hollow glass beads to the alkaline solution is (5-30): 100;
the temperature of the drying is 80-120 ℃;
the drying time is 3-5 h.
6. The method according to claim 4, wherein the step 2) is specifically:
premixing hydrocarbon solvent and styrene under the condition of nitrogen to obtain premix, adding an organic lithium initiator into the premix for polymerization reaction, adding butadiene for polymerization again, adding a bifunctional coupling agent for coupling reaction, adding an anti-aging agent after terminating the reaction, adding the hollow glass beads subjected to surface hydroxylation obtained in the steps for mixing, and finally performing cyclone dispersion and drying to obtain the composite hollow glass beads.
7. The method of claim 6, wherein the hydrocarbon solvent comprises cyclohexane;
the mass ratio of the hydrocarbon solvent to the styrene is (0.5-1.5): 1, a step of;
the temperature of the premixing is 40-80 ℃;
the organolithium initiator comprises n-butyllithium;
the mass ratio of the organic lithium initiator to the premix is (0.5-3): 100;
the temperature of the polymerization reaction is 40-80 ℃;
the polymerization reaction time is 10-60 min.
8. The preparation method according to claim 6, wherein the mass ratio of butadiene to styrene is (50-60): 100;
the temperature of the repolymerization is 40-80 ℃;
the time for the repolymerization is 10-50 min;
the difunctional coupling agent comprises epichlorohydrin;
the mass ratio of the difunctional coupling agent to the styrene is (5-20): 100;
the coupling reaction time is 10-30 min.
9. The method of claim 6, wherein the anti-aging agent comprises 2, 6-di-t-butyl-p-cresol;
the mass ratio of the anti-aging agent to the reaction system after the coupling reaction is (0.5-3): 100;
the mass ratio of the hollow glass beads to the reaction system after the coupling reaction is (10-50): 100;
the mixing time is 10-30 min;
the mixing step further comprises a raffinate separation step;
the cyclone dispersing time is 10-30 min;
the drying temperature is 60-100 ℃.
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