CN117624624A - Grafted glass bead, preparation method, polypropylene composite material and application - Google Patents
Grafted glass bead, preparation method, polypropylene composite material and application Download PDFInfo
- Publication number
- CN117624624A CN117624624A CN202311594051.7A CN202311594051A CN117624624A CN 117624624 A CN117624624 A CN 117624624A CN 202311594051 A CN202311594051 A CN 202311594051A CN 117624624 A CN117624624 A CN 117624624A
- Authority
- CN
- China
- Prior art keywords
- ppr
- grafted
- glass beads
- hollow glass
- hgs
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 112
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 112
- -1 preparation method Substances 0.000 title claims abstract description 68
- 239000011521 glass Substances 0.000 title claims abstract description 65
- 239000011324 bead Substances 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000007112 amidation reaction Methods 0.000 claims abstract description 11
- 238000009413 insulation Methods 0.000 claims abstract description 11
- 125000003277 amino group Chemical group 0.000 claims abstract description 4
- 230000004048 modification Effects 0.000 claims description 31
- 238000012986 modification Methods 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 23
- 239000003963 antioxidant agent Substances 0.000 claims description 19
- 230000003078 antioxidant effect Effects 0.000 claims description 19
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 14
- 239000007822 coupling agent Substances 0.000 claims description 10
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 10
- 239000011325 microbead Substances 0.000 claims description 9
- 229920005604 random copolymer Polymers 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 238000001746 injection moulding Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- VXZFIWMLIIIYMF-UHFFFAOYSA-N N'-(4-trimethylsilyloxypentyl)ethane-1,2-diamine Chemical compound NCCNCCCC(C)O[Si](C)(C)C VXZFIWMLIIIYMF-UHFFFAOYSA-N 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000005453 pelletization Methods 0.000 claims 1
- 238000009434 installation Methods 0.000 abstract description 6
- 125000005395 methacrylic acid group Chemical group 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 230000009435 amidation Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 22
- 239000004033 plastic Substances 0.000 description 13
- 229920003023 plastic Polymers 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 9
- 238000010998 test method Methods 0.000 description 8
- 239000004005 microsphere Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000004321 preservation Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- 101000751233 Halobacterium salinarum (strain ATCC 700922 / JCM 11081 / NRC-1) 50S ribosomal protein L21e Proteins 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000004595 color masterbatch Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides grafted glass beads, a preparation method thereof, a polypropylene composite material and application. The grafted glass beads comprise NH 2 HGS and coating on NH 2 -a PPR layer on the HGS surface, wherein the PPR layer is predominantly grafted with the NH via methacrylic groups grafted on PPR-g-MA 2 -covalent bonding by amidation of the amino groups on the HGS; thus, the PPR layer and the PPR matrix coated on the grafted glass bead are intactThe polypropylene composite material prepared by the method has the characteristics of lower density, better heat-resistant stability, lower heat conductivity coefficient and the like, and simultaneously has better mechanical property. The heat-insulating pipe made of the polypropylene composite material can greatly reduce heat loss and pipeline installation strength. Therefore, the invention also provides application of the grafted glass beads in preparing polypropylene composite materials and heat-insulation pipes.
Description
Technical Field
The invention belongs to the technical field of plastic pipelines, and particularly relates to grafted glass beads, a preparation method thereof, a polypropylene composite material and application.
Background
With the improvement of the living standard of people, the development of science and technology and the enhancement of energy conservation consciousness, the heating system is correspondingly changed greatly. The application of the plastic pipe in the heating system promotes the development of heating industry, the plastic pipe gradually replaces the metal pipe and is a necessary result of technological development, and compared with the traditional metal pipe, the plastic heating pipe has the advantages of light weight, corrosion resistance, no scaling, easy installation and maintenance, long service life, reasonable cost performance, attractive appearance and the like, and the energy consumption during conveying the heating medium is greatly reduced due to the smooth inner surface.
PPR (polypropylene random) also called as random copolymer polypropylene (PPR), the product has good toughness, high strength, excellent processability, good creep resistance at higher temperature and high transparency. Compared with the traditional cast iron pipe, galvanized steel pipe, cement pipe and other pipelines, the PPR has the advantages of energy conservation, material saving, environmental protection, light weight, high strength, corrosion resistance, smooth inner wall, no scaling, simple construction and maintenance, long service life and the like, and is an excellent material for cold and hot water conveying pipes.
Chinese patent application CN116063797 a discloses a polypropylene composition, a polypropylene material and a pressure pipe, the polypropylene composition comprising a random copolymer polypropylene, an alpha-crystal form nucleating agent, an antioxidant, a light stabilizer, an optional color masterbatch and an optional acid absorber; wherein the alpha-crystal form nucleating agent is used in an amount of 0.01 to 0.3 parts by weight relative to 100 parts by weight of the random copolymer polypropylene. The pressure pipeline made of the polypropylene composition or the polypropylene material disclosed in the patent application has the advantages of good long-term hydrostatic thermal stability, high yield stress, high load deformation temperature, high tensile strength and the like.
However, the polypropylene pressure pipe still causes a great deal of heat loss in hot water transmission, and the on-site handling and installing of the pipe consumes a great deal of manpower.
Disclosure of Invention
In view of the above, the invention aims to mainly solve the problems of high heat conduction efficiency, high labor intensity for long-term transportation and installation and the like of PPR pipes in the prior art, and provides a grafted glass bead and a preparation method thereof. Therefore, the polypropylene composite material prepared from the grafted glass beads has the characteristics of lower density, better heat-resistant stability, lower heat conductivity coefficient and the like, and also has better mechanical properties. Therefore, the heat-insulating pipe manufactured by the polypropylene composite material can greatly reduce heat loss and pipeline installation strength.
To achieve the above object, the present invention provides, in a first aspect, a grafted glass bead comprising an aminated hollow glass bead (NH 2 -HGS) and coating on NH 2 -a PPR layer of the HGS surface, wherein the PPR layer is mainly formed by methacrylic acidGrafting methacrylic groups grafted onto PPR (PPR-g-MA) with the NH 2 The amino groups on HGS undergo covalent bonding by amidation reaction.
The second aspect of the invention provides a method for preparing the grafted glass beads, comprising the following steps:
first modification: adopting a siloxane coupling agent to carry out modification treatment on HGS to obtain NH 2 -HGS；
And (3) secondary modification: ppr-g-MA with the NH 2 And (3) carrying out amidation reaction on the HGS to enable the PPR to be grafted to the HGS surface through a covalent bond, and forming a layer of PPR on the HGS surface.
The third aspect of the invention provides a polypropylene composite material, which is mainly prepared by blending, extruding and granulating a random copolymer polypropylene (PPR) substrate, an antioxidant and the grafted glass beads. Wherein the mass ratio of the grafted glass beads to the PPR to the antioxidant is (5-20): 78-95): 0.2-0.4.
The fourth aspect of the invention provides a thermal insulation pipe made of the polypropylene composite material. The heat preservation pipe is mainly prepared from the polypropylene composite material through injection molding.
Therefore, the grafted glass bead and the preparation method thereof provided by the invention utilize methacrylic acid grafted PPR (PPR-g-MA) to modify the hollow glass bead (HGS) so that the surface of the HGS is coated with a layer of PPR, thus being beneficial to integrating with a PPR matrix, enhancing the interface combination of the hollow glass bead and the PPR, greatly reducing the density of the polypropylene plastic pipe while ensuring the mechanical property of the PPR composite pipe, increasing the heat-resistant stability of the pipe and reducing the heat conductivity coefficient of the pipe.
The modified layer PPR on the grafted glass beads can be tightly combined with the hollow glass beads and can be fused with a raw material PPR base material of the polypropylene composite material, so that the prepared composite material has the characteristics of light weight, good thermal stability, low heat conductivity coefficient and the like, and the mechanical property of the polypropylene material can be improved.
The polypropylene heat-insulating pipe provided by the invention is prepared from the polypropylene composite material, has the characteristics of low linear expansion coefficient, high mechanical strength, longitudinal retraction rate and the like, can be used as a cold and hot water conveying pipe, reduces heat loss in the heat transmission process, and reduces the labor intensity of pipe conveying and installation.
Detailed Description
The terms used in the invention are all common terms in the art, and raw materials, equipment, preparation process, test method and the like used are all prior art in the art without special description.
In a first aspect, the present invention provides a grafted glass bead comprising an aminated hollow glass bead (NH 2 -HGS) and coating on NH 2 -a PPR layer on the HGS surface, wherein the PPR layer is mainly grafted with the NH by methacrylic acid groups grafted onto methacrylic acid grafted PPR (PPR-g-MA) 2 The amino groups on HGS undergo covalent bonding by amidation reaction.
The HGS has smaller true density and smaller strength, while being favorable for improving the heat conducting property of the polypropylene composite material when the grain diameter is larger; the opposite is the case; thus, in combination, the HGS preferably has a true density of 0.3 to 0.6 g/cm 3 Such as 0.3, 0.4, 0.45, 0.5, 0.55, 0.6 g/cm 3 Etc.; the particle size of HGS is preferably 20 to 85. Mu.m. The HGS may be HGS of model number HL30, HL40, HL50 or HL60, etc. manufactured by Santa Clay cenosphere New Material Co.Ltd.
In the present invention, the density of PPR used is preferably 0.91 to 0.93 g/cm 3 . The mass percent of MA groups in PPR-g-MA is preferably about 20%, and the PPR-g-MA is prepared by adopting the existing method, which comprises the steps of taking PPR, dimethylbenzene (solvent), benzoyl peroxide (initiator) and Methacrylic Acid (MA) as raw materials, and carrying out polymerization reaction on the PPR and the methacrylic acid to prepare the graft PPR-g-MA. Specifically, PPR and dimethylbenzene are added into a four-neck flask, the mixture is heated to 180 ℃ and stirred in a nitrogen atmosphere, benzoyl peroxide and methacrylic acid are added dropwise at 120 ℃ after the PPR is completely dissolved, 2.5h is reacted, and the reactant is poured into methanol while the mixture is hot, so that white floccule precipitate is obtainedFiltering with a Buchner funnel, extracting with acetone in a Soxhlet filter for 10h, and vacuum filtering and drying to obtain graft ppr-g-MA; preferably, MA is added in an amount of 1/4 of the added mass of PPR.
The aminated HGS is preferably a siloxane coupling agent modified HGS, wherein the siloxane coupling agent is aminopropyl triethoxysilane (APTES), N-beta- (aminoethyl) -gamma-aminopropyl methyldimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl trimethylethoxysilane.
The second aspect of the invention provides a method for preparing the grafted glass beads, comprising the following steps:
first modification: adopting a siloxane coupling agent to carry out modification treatment on HGS to obtain NH 2 -HGS；
And (3) secondary modification: ppr-g-MA with the NH 2 And (3) carrying out amidation reaction on the HGS to enable the PPR to be grafted to the HGS surface through a covalent bond, and forming a layer of PPR on the HGS surface.
The first modification step comprises the following steps: the siloxane coupling agent and HGS are subjected to reflux reaction at 70-90 ℃ for 3-4 h according to the mass ratio of 1 (1-4) under the environment of pH value of 4.7-5.5, washed to be neutral, and dried to obtain the NH 2 -HGS. Wherein, the mass ratio of HGS to the siloxane coupling agent can be 1:1, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, and the like, and is preferably 1 (2-3). The reflux temperature may be 70 ℃, 75 ℃,80 ℃, 85 ℃, 90 ℃, etc.
The secondary modification step comprises the following steps: grafting MA onto PPR to form PPR-g-MA; and then the NH is added 2 The HGS and ppr-g-MA are amidated according to the mass ratio of 1 (1-4) at 110-140 ℃ for 2-4 h, so that MA groups and NH in ppr-g-MA 2 And (3) amidation reaction of amino in the HGS, wherein a PPR group in PPR-g-MA is connected with the HGS through a covalent bond, so that the grafted glass microsphere is prepared. Wherein the amidation reaction temperature may be 110℃at 120℃at 130℃at 140℃and preferably 120℃to 130 ℃.
When NH 2 When the amount of HGS is relatively large, the grafting amount of ppr-g-MA is small, and the optimal modification effect cannot be achieved; when the amount of ppr-g-MA is relatively large, the amount of ppr-g-MA grafted is largeIs in saturation, so that raw materials are wasted; therefore, NH 2 The mass ratio of HGS to ppr-g-MA is preferably 1 (1-4), such as 1:1, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, etc., more preferably 1 (2-3).
The third aspect of the invention provides a polypropylene composite material, which is mainly prepared by blending, extruding and granulating a random copolymer polypropylene (PPR) substrate, an antioxidant and the grafted glass beads. The mass ratio of the grafted glass bead to the PPR to the antioxidant is preferably (5-20): (78-95): (0.2-0.4), more preferably, the total mass parts of the grafted glass bead, the PPR and the antioxidant is 100 parts, such as 5:94.7:0.3, 7:92.8:0.2, 10:89.6:0.4, 12:87.8:0.2, 15:84.7:0.3, 18:81.7:0.3, 18:81.8:0.2, 20:79.7:0.3, 19:80.6:0.4, and the like. The density of the PPR base material is preferably 0.91-0.93 g/cm 3 。
The antioxidant is one or a combination of more of antioxidant B215, antioxidant 1010, antioxidant 1076 and antioxidant B225.
The method for blending extrusion granulation comprises the following steps: the PPR base material and the antioxidant are mixed uniformly in a high-speed mixer, then the grafted glass beads are added for melt blending, and then the granulation is carried out by adopting a double-screw extrusion granulation process, and the product is obtained after drying. Wherein, the technological parameters of double screw extrusion granulation are as follows: the processing temperature is 200-220 ℃, and the rotating speed of the twin-screw is 50-150 r/min.
The fourth aspect of the invention provides a thermal insulation pipe made of the polypropylene composite material. The heat preservation pipe is mainly prepared by injection molding of the polypropylene composite material, wherein the injection molding temperature is 195-205 ℃, and the injection pressure is 35-40 MPa.
In the invention, the density of the polypropylene heat-insulation pipe is 0.72-0.91 g/cm 3 The heat conductivity coefficient is 0.165-0.225W m -1 ·k -1 Bending strength 32.02-36.88 MPa, tensile strength 22.72-30.32 MPa, notched impact strength 3.40-4.56 KJ m -2 The longitudinal retraction rate is 0.52 to 0.69 percent, and the linear expansion coefficient is 8.17 multiplied by 10 -5 ～9.35×10 -5 m·m -1 ·℃ -1 。
The method for testing the performance of the heat preservation pipe comprises the following steps:
the density testing method refers to the standard of GB/T1033.1-2008 determination of the density of plastic non-foamed plastics;
the heat conductivity coefficient test method refers to a heat protection flat plate method of a plastic heat conductivity coefficient test method of GB 3399-1982;
the tensile strength test method refers to GB/T1040.1-2006 test of plastic tensile properties;
the bending strength test method refers to GB/T9341-2008 test of plastic bending property;
notched impact Strength test method reference GB/T1043.1-2008 determination of impact Property of Plastic simply supported Beam part 1: non-instrumented impact experiments;
the longitudinal retraction rate test method refers to the standard of GB/T6671-2001 thermoplastic plastic pipe longitudinal retraction rate determination;
the linear expansion coefficient test method refers to the quartz dilatometer method for measuring the linear expansion coefficient of GB/T1036-2008 plastics at the temperature of-30 ℃ to 30 ℃.
The hollow glass beads used in the examples below were all from new materials, inc. of Santa Clay hollow beads, zhengzhou, and the technical scheme of the present invention is described in further detail by way of specific embodiments.
Example 1
(1) Preparation of NH by first modification 2 -HGS: 25 parts of HGS model HL30 was added to a flask containing an ethanol solution, and acetic acid was then added dropwise to adjust the pH of the solution to=5. Then, a solution containing 75 parts of APTESA (75 parts of APTESA was added thereto), and the mixture was stirred at room temperature for 15 minutes. Adding hollow glass beads into the solution, stirring and refluxing at 80deg.C for reaction 3 h, centrifuging, alternately washing with ethanol and distilled water to neutrality, and vacuum drying at 80deg.C for 5h to obtain NH 2 -HGS。
(2) Preparing grafted glass beads through secondary modification: adding PPR and dimethylbenzene into a four-neck flask, heating to 180 ℃ in nitrogen atmosphere, stirring, dropwise adding benzoyl peroxide and MA with the mass of 1/4 of that of the PPR at 120 ℃ after the PPR is completely dissolved, reacting for 2.5h, and heatingThe reaction was poured into methanol to give a white flocculent precipitate, which was filtered with a buchner funnel and extracted with acetone in a Soxhlet filter for 10h, and finally dried by suction filtration to give the graft ppr-g-MA. 75 parts of ppr-g-MA are dissolved in xylene and stirred at 120 ℃. Next, 25 parts of NH was added 2 HGS, reaction 3 h at 120 ℃. And extracting the hollow glass beads after the reaction with dimethylbenzene for 3 times, and vacuum drying for 5 hours at the temperature of 100 ℃ to obtain the random copolymer polypropylene grafted hollow glass bead material.
(3) Preparing a polypropylene composite material: 94.8 parts of PPR base material and 0.2 part of antioxidant B215 are mixed uniformly in a high-speed mixer (40 r/min) and added from a main feeding port. And (3) adjusting the main side feeding proportion to enable 5 parts of random copolymer polypropylene grafted hollow glass microsphere material to be added from a side feeding port. The processing temperature of the double screw extruder is 200-220 ℃, and the rotating speed of the double screw is 50-150 r/min, so as to prepare the PPR/HGS composite material.
(4) Preparing a heat preservation pipe: the PPR/HGS composite material is dried in a vacuum drying oven for 12 h after being pelletized, and then is made into a random copolymer polypropylene plastic heat preservation pipe S1 by an injection molding machine, wherein the injection molding temperature is 195-205 ℃, and the injection pressure is 35-40 MPa.
Example 2
This embodiment is substantially the same as embodiment 1, with the main differences that: (1) Preparation of NH by first modification 2 The model of HGS adopted in the HGS is HL40; (3) The polypropylene composite material is prepared by different raw material proportions, in the embodiment, 89.7 parts of PPR base material, 0.3 part of antioxidant 1010 and 10 parts of grafted hollow glass microsphere material; the rest raw materials and the process steps are unchanged, and the polypropylene heat-preserving pipe S2 is prepared.
Example 3
This embodiment is substantially the same as embodiment 1, with the main differences that: (1) Preparation of NH by first modification 2 The model of HGS adopted in the HGS is HL50; (3) The polypropylene composite material is prepared by different raw material proportions, in the embodiment, 84.6 parts of PPR base material, 0.4 part of antioxidant 1076 and 15 parts of grafted hollow glass microsphere material; the rest raw materials and the process steps are unchanged, and the polypropylene heat-preserving pipe S3 is prepared.
Example 4
This embodiment is substantially the same as embodiment 1, with the main differences that: (1) Preparation of NH by first modification 2 In the step of HGS, the model of HGS is HL60; (3) The polypropylene composite material is prepared by different raw material proportions, in the embodiment, 79.7 parts of PPR base material, 0.3 part of antioxidant B225 and 20 parts of grafted hollow glass microsphere material; the rest raw materials and the process steps are unchanged, and the polypropylene heat-preserving pipe S4 is prepared.
Example 5
This embodiment is substantially the same as embodiment 1, with the main differences that: (1) Preparation of NH by first modification 2 In the step of HGS, 50 parts of HGS with model HL30 and 50 parts of solution containing APTES are taken as raw materials; (2) In the step of preparing the grafted glass beads by secondary modification, 50 parts of ppr-g-MA and 50 parts of NH are adopted 2 -HGS; the rest raw materials and the process steps are unchanged, and the polypropylene heat-preserving pipe S5 is prepared.
Example 6
This embodiment is substantially the same as embodiment 3, with the main differences that: (1) Preparation of NH by first modification 2 In the step of HGS, 20 parts of HGS with model HL50 and a solution containing 80 parts of APTES are taken as raw materials; (2) In the step of preparing the grafted glass beads by secondary modification, 80 parts of ppr-g-MA and 20 parts of NH are adopted 2 -HGS; the rest raw materials and the process steps are unchanged, and the polypropylene heat-preserving pipe S6 is prepared.
Example 7
This embodiment is substantially the same as embodiment 3, with the main differences that: (2) In the step of preparing the grafted glass beads by secondary modification, 50 parts of ppr-g-MA and 50 parts of NH are adopted 2 -HGS; the rest raw materials and the process steps are unchanged, and the polypropylene heat-preserving pipe S7 is prepared.
Example 8
This embodiment is substantially the same as embodiment 3, with the main differences that: (2) In the step of preparing the grafted glass beads by secondary modification, 60 parts of ppr-g-MA and 20 parts of NH are adopted 2 -HGS; the rest raw materials and the process steps are unchanged, and the polypropylene heat-preserving pipe S8 is prepared.
Comparative example 1
This comparative example and example 3 baseThe main difference is that: omitting the step of (2) preparing grafted glass beads by secondary modification, and (3) preparing polypropylene composite material, wherein the modified glass beads added in the step are NH 2 HGS, and 45 parts ppr-g-MA were added; the rest raw materials and the process steps are unchanged, and the polypropylene heat-insulation pipe D1 is prepared.
Comparative example 2
This comparative example is substantially the same as example 3, with the main difference that: (2) In the step of preparing the grafted glass beads by secondary modification, 40 parts of ppr-g-MA and 60 parts of NH are adopted 2 -HGS; the rest raw materials and the process steps are unchanged, and the polypropylene heat-insulation pipe D2 is prepared.
Comparative example 3
This comparative example is substantially the same as example 3, with the main difference that: in the comparative example, the unmodified HGS is directly used as the raw material for preparing the polypropylene composite material (3), namely (1) the first modification for preparing NH is omitted 2 -HGS and (2) a step of secondary modification to prepare grafted glass microbeads; the rest raw materials and the process steps are unchanged, and the polypropylene heat-insulation pipe D3 is prepared.
Comparative example 4
This comparative example is substantially the same as example 3, with the main difference that: in the process of preparing the polypropylene heat-insulation pipe in the comparative example, HGS is not added, and the raw materials comprise 99.7 parts of PPR base material and 0.3 part of antioxidant B215, and other raw materials and process parameters are unchanged, so that the polypropylene heat-insulation pipe D4 is prepared.
Performance testing
The examples and comparative examples were prepared as standard standards for testing, and the density, thermal conductivity, flexural strength, notched impact strength, longitudinal retractive force and linear expansion coefficient were measured at 25℃to obtain the results shown in Table 1 below.
TABLE 1 Polypropylene pipe Performance test results Table
From the data for polypropylene tubing S3 and D1, it can be seen that: compared with the independent addition of the microbeads and the ppr-g-MA, the addition of the ppr-g-MA grafted microbeads can better improve the mechanical properties of the pipe and reduce the longitudinal retraction rate and the linear expansion coefficient of the pipe.
From the data for polypropylene tubing S3 and D2, it can be seen that: the density and the heat conduction of the two are equivalent, but the mechanical property of S3 is higher than D2, and the longitudinal retraction rate and the linear expansion coefficient are lower than D2. Mainly because of the small grafting amount of ppr-g-MAA in D2, the optimal modification effect cannot be achieved.
From the data for polypropylene tubing S3, D3 and D4, it can be seen that: the density and the heat conductivity coefficient of the modified microsphere are equivalent, and compared with D3, S3 has higher mechanical property, lower longitudinal retraction rate and linear expansion coefficient, which is mainly caused by the fact that the unmodified microsphere has smooth surface, higher chemical inertia and poor bonding property with a matrix interface. S3 has a lower density and thermal conductivity than D4, which is determined primarily by the low density, low thermal conductivity properties of the microbeads themselves.
Thus, it can be seen from the data of the polypropylene pipes S1 to S8 and D1 to D4:
(1) The density and the heat conductivity coefficient of the pipe can be well reduced by adding the hollow glass beads;
(2) The ppr-g-MA grafting modification of the microbeads can obviously improve the influence of the microbeads on the mechanical properties of the tube
(3) The modification effect is best when the mass ratio of ppr-g-MA to HGS is 3:1.
Therefore, the polypropylene heat-insulating pipe provided by the embodiment of the invention has the characteristics of low linear expansion coefficient, high mechanical strength, longitudinal retraction rate and the like, can be used as a cold and hot water conveying pipe, reduces heat loss in the heat transmission process, and reduces the labor intensity of pipe conveying and installation.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same; while the invention has been described in detail with reference to the preferred embodiments, those skilled in the art will appreciate that: modifications may be made to the specific embodiments of the present invention or equivalents may be substituted for part of the technical features thereof; without departing from the spirit of the invention, it is intended to cover the scope of the invention as claimed.
Claims (10)
1. The grafted glass bead is characterized by comprising an aminated hollow glass bead and a PPR layer coated on the surface of the aminated hollow glass bead, wherein the PPR layer is mainly connected with an amino group on the aminated hollow glass bead through a covalent bond formed by amidation reaction of methacrylic acid grafted on methacrylic acid grafted PPR.
2. The grafted glass microbead according to claim 1, wherein the true density of the hollow glass microbead is 0.3-0.6 g/cm 3 The grain diameter is 20-85 mu m.
3. A method of making the grafted glass microbead of claim 1 or 2, comprising:
first modification: adopting siloxane coupling agent as hollow glass bead to make modification treatment so as to obtain the amino-ized hollow glass bead;
and (3) secondary modification: and carrying out amidation reaction on the methacrylic acid grafted PPR and the aminated hollow glass beads, so that the PPR groups in the methacrylic acid grafted PPR are grafted to the surfaces of the hollow glass beads through covalent bonds, and a PPR layer is formed on the surfaces of the hollow glass beads.
4. A method of preparing according to claim 3, wherein the step of first modifying comprises: the siloxane coupling agent and the hollow glass beads are subjected to reflux reaction at 70-90 ℃ for 3-4 h according to the mass ratio of 1 (1-4) under the environment that the pH value is 4.7-5.5, washed to be neutral, and dried to obtain the aminated hollow glass beads;
preferably, the mass ratio of the hollow glass beads to the siloxane coupling agent is 1 (2-3).
5. The method of claim 3 or 4, wherein the step of secondarily modifying comprises: amidation reaction is carried out on the aminated hollow glass beads and methacrylic acid grafted PPR according to the mass ratio of 1 (1-4) at 110-140 ℃ for 2-4 h, so as to obtain the grafted glass beads;
preferably, the amidation reaction temperature is 120℃to 130 ℃.
6. The method of claim 3 or 4, wherein the siloxane coupling agent is aminopropyl triethoxysilane, N- β - (aminoethyl) - γ -aminopropyl methyldimethoxysilane, or N- (β -aminoethyl) - γ -aminopropyl trimethylethoxysilane.
7. The polypropylene composite material is characterized by being prepared by blending, extruding and granulating a random copolymer polypropylene base material, an antioxidant and the grafted glass beads according to claim 1 or 2;
preferably, the mass ratio of the grafted glass beads to the PPR to the antioxidant is (5-20): 78-95): 0.2-0.4;
preferably, the density of the PPR base material is 0.91-0.93 g/cm 3 。
8. The polypropylene composite of claim 7, wherein the method of blending extrusion pelletization comprises: uniformly mixing the PPR base material and the antioxidant in a high-speed mixer, adding the grafted glass beads for melt blending, granulating by adopting a double-screw extrusion granulating process, and drying;
preferably, the technological parameters of the twin-screw extrusion granulation are as follows: the processing temperature is 200-220 ℃, and the rotating speed of the twin-screw is 50-150 r/min.
9. The polypropylene composite of claim 7, wherein the antioxidant is a combination of one or more of antioxidant B215, antioxidant 1010, antioxidant 1076, and antioxidant B225.
10. A thermal insulation tubing made from the polypropylene composite of claim 7 or 8 or 9;
preferably, the thermal insulation pipe is manufactured by adopting an injection molding method;
preferably, the injection molding temperature is 195-205 ℃, and the injection pressure is 35-40 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311594051.7A CN117624624A (en) | 2023-11-27 | 2023-11-27 | Grafted glass bead, preparation method, polypropylene composite material and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311594051.7A CN117624624A (en) | 2023-11-27 | 2023-11-27 | Grafted glass bead, preparation method, polypropylene composite material and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117624624A true CN117624624A (en) | 2024-03-01 |
Family
ID=90017489
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311594051.7A Pending CN117624624A (en) | 2023-11-27 | 2023-11-27 | Grafted glass bead, preparation method, polypropylene composite material and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117624624A (en) |
-
2023
- 2023-11-27 CN CN202311594051.7A patent/CN117624624A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101423733B (en) | Method for preparing transparent hot melt adhesive for PP-R plastic-aluminum steady state tube | |
| CN103172937B (en) | A kind of Silane Grafted PPR pipe PP Pipe Compound and preparation method thereof | |
| CN105778296B (en) | A kind of cold-resistant PP-R pipe and preparation method thereof | |
| CN108003475B (en) | Heat-resistant reinforced polypropylene pipe and preparation method thereof | |
| WO2022095363A1 (en) | Polycarbonate alloy composition, preparation method therefor and application thereof | |
| CN117624624A (en) | Grafted glass bead, preparation method, polypropylene composite material and application | |
| CN109679243B (en) | Heat-resistant corrosion-resistant polyvinyl chloride water supply and drainage pipe and preparation method thereof | |
| CN117567813A (en) | Bamboo-wood fiber composite wallboard and preparation method thereof | |
| CN115011018B (en) | PE gas pipe and preparation method thereof | |
| CN114440012B (en) | Polypropylene composite pipe and preparation method and application thereof | |
| CN109265786A (en) | A kind of UHMWPE composite material and preparation method of high thermal conductivity | |
| KR20100002408A (en) | Thermoplastic resin | |
| CN113980462A (en) | Hydrolysis-resistant light corrugated pipe and processing technology thereof | |
| CN115490949B (en) | PEXb tubular product with high shape memory function | |
| CN105176209B (en) | High intensity low thermal conductivity PP composite material layer for pipe insulation | |
| CN112123907A (en) | Polytetrafluoroethylene/polypropylene film composite polyvinyl chloride plastic sheet | |
| CN113845735B (en) | Polypropylene composite material resistant to thermal aging and preparation method thereof | |
| CN110713678A (en) | Preparation method of high-strength pipe for double-wall corrugated pipe | |
| CN110791040A (en) | Nano calcium carbonate for toughening PVC (polyvinyl chloride) and preparation method thereof | |
| CN117362799B (en) | High-temperature-resistant modified PE water supply pipe and preparation method thereof | |
| CN113831620B (en) | High heat-resistant creep-resistant pipe composition and preparation method thereof | |
| CN109852296B (en) | Hot melt adhesive and application thereof in PVC (polyvinyl chloride) lining plastic steel pipe | |
| CN115651204B (en) | N-carbonyl-bisamide-polyolefin compound, and preparation method and application thereof | |
| CN109595498B (en) | Municipal administration illumination LED street lamp | |
| CN116836469A (en) | Modified PE pipe with enhanced scratch resistance and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |