CN117430937B - Polycarbonate modified plastic for limiting ambient temperature and preparation method thereof - Google Patents
Polycarbonate modified plastic for limiting ambient temperature and preparation method thereof Download PDFInfo
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- CN117430937B CN117430937B CN202311581388.4A CN202311581388A CN117430937B CN 117430937 B CN117430937 B CN 117430937B CN 202311581388 A CN202311581388 A CN 202311581388A CN 117430937 B CN117430937 B CN 117430937B
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- 239000004417 polycarbonate Substances 0.000 title claims abstract description 48
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 45
- 239000004033 plastic Substances 0.000 title claims abstract description 33
- 229920003023 plastic Polymers 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 27
- 229920005668 polycarbonate resin Polymers 0.000 claims abstract description 48
- 239000004431 polycarbonate resin Substances 0.000 claims abstract description 48
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 39
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- 229920006150 hyperbranched polyester Polymers 0.000 claims abstract description 26
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 21
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 21
- 239000003063 flame retardant Substances 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 19
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 17
- 239000004611 light stabiliser Substances 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 7
- 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 7
- 238000001125 extrusion Methods 0.000 claims description 7
- 230000003179 granulation Effects 0.000 claims description 7
- 238000005469 granulation Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- OWBLFTIPFLNLBN-UHFFFAOYSA-N 2-hydroxy-1,3,2$l^{5}-benzodioxaphosphole 2-oxide Chemical compound C1=CC=C2OP(O)(=O)OC2=C1 OWBLFTIPFLNLBN-UHFFFAOYSA-N 0.000 claims description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 2
- 150000008301 phosphite esters Chemical class 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 6
- 239000000654 additive Substances 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 34
- -1 polysiloxane chain Polymers 0.000 description 28
- 239000004359 castor oil Substances 0.000 description 21
- 235000019438 castor oil Nutrition 0.000 description 21
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 21
- 229920005862 polyol Polymers 0.000 description 18
- 150000003077 polyols Chemical class 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000003208 petroleum Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 229910000104 sodium hydride Inorganic materials 0.000 description 6
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 5
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 4
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UUNGBOQAZQUJMZ-UHFFFAOYSA-N 3-bromopropyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CCCBr UUNGBOQAZQUJMZ-UHFFFAOYSA-N 0.000 description 3
- 238000012650 click reaction Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- YORCIIVHUBAYBQ-UHFFFAOYSA-N propargyl bromide Chemical compound BrCC#C YORCIIVHUBAYBQ-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- ZLSOONVQLWLPMF-UHFFFAOYSA-M 3-(3,8-diamino-6-phenylphenanthridin-5-ium-5-yl)propyl-diethyl-methylazanium;dibromide Chemical compound [Br-].[Br-].C12=CC(N)=CC=C2C2=CC=C(N)C=C2[N+](CCC[N+](C)(CC)CC)=C1C1=CC=CC=C1 ZLSOONVQLWLPMF-UHFFFAOYSA-M 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 2
- 239000005052 trichlorosilane Substances 0.000 description 2
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses a polycarbonate modified plastic for limiting ambient temperature and a preparation method thereof. The composite material is prepared from the following components in parts by weight: 38-58% of siloxane copolymerized polycarbonate resin, 38-58% of polycarbonate resin, 2-4% of silsesquioxane end-capped star hyperbranched polyester, 0.1-1% of flame retardant, 0.01-1% of antioxidant, 0.01-1% of light stabilizer and 0.01-1% of other auxiliary agents. The invention adopts specific siloxane copolycarbonate resin and specific polycarbonate to compound in a specific mass ratio, and after silsesquioxane end-capped star-shaped hyperbranched polyester additive is added, the invention increases the free volume of molecular chain movement in the system, improves the compatibility with the siloxane copolycarbonate resin and the polycarbonate in the system, reduces the interfacial tension and improves the low-temperature and impact resistance of the polycarbonate composite material.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to polycarbonate modified plastic for limiting ambient temperature and a preparation method thereof.
Background
Polycarbonates (PCs) are widely used in the field of special materials because of their excellent impact strength, heat resistance and low temperature resistance. However, the existing PC composite material has the problem that the molecular chain is extremely easy to break at the limit environmental temperature due to the secondary transformation of PC at low temperature, and the product is cracked macroscopically, which severely limits the application of PC at the limit environmental temperature.
Polycarbonates (PCs) and their blends are a unique class of engineering plastics. With the expansion of application environment, conventional polycarbonates are increasingly difficult to meet good impact toughness at extreme environmental temperatures, and as current polymer manufacturers are increasingly conservative in developing and commercializing new polymers, modification of existing PCs is an effective way to achieve performance to meet increasingly demanding application environment requirements.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art and provides a polycarbonate modified plastic for limiting ambient temperature and a preparation method thereof.
The invention provides polycarbonate modified plastic for limiting ambient temperature, which is prepared from the following components in parts by weight:
38-58% of siloxane copolymerized polycarbonate resin (mass ratio, the same applies below), 38-58% of polycarbonate resin, 2-4% of silsesquioxane end-capped star hyperbranched polyester, 0.1-1% of flame retardant, 0.01-1% of antioxidant, 0.01-1% of light stabilizer and 0.01-1% of other auxiliary agents;
Wherein the siloxane copolycarbonate resin is CH9115; the polysiloxane chain is purchased from Cangzhou Massa corporation, the relative molecular weight is 24000, the average phase area size of the polysiloxane chain segment is 30-60 nm, and the mass melt flow rate is 9-12 g/10min at 300 ℃/1.2 kg;
the polycarbonate resin is A1105, purchased from Wanhua chemical company;
The silsesquioxane-capped star-shaped hyperbranched polyester is autonomously synthesized by utilizing click chemistry.
The flame retardant is at least one of polysilabone flame retardant and phenylene phosphate flame retardant.
The antioxidant is at least one of acrylic acid ester antioxidants and phosphite ester antioxidants.
The light stabilizer is one or a mixture of UV234, UV981, UV-329 and UV-360;
The other auxiliary agents are black master batches.
Specifically, the antioxidant is a compound of antioxidant 168 and antioxidant 1010, and the weight ratio of the compound is 1:1, a step of;
The light stabilizer is a compound of UV981 and UV-329, and the compound weight ratio is 1:1, a step of;
The flame retardant is PX-200;
The other auxiliary agents are black master batches.
The structural formula of the silsesquioxane-terminated star-shaped hyperbranched polyester is as follows:
The silsesquioxane-terminated star-shaped hyperbranched polyester is prepared by the following steps:
(1) Castor oil-based hyperbranched polyol shown in formula 1 is synthesized by taking castor oil and 2, 2-dimethylolpropionic acid as raw materials;
(2) Synthesizing heptaphenyl trisilanol sodium salt as a precursor for synthesizing phenyl POSS, reacting with 3-bromopropyl trichlorosilane, and reacting the obtained product with sodium azide to obtain 3-azidopropyl heptaphenyl POSS shown in formula 2;
(3) The castor oil-based hyperbranched polyol is reacted with propargyl bromide firstly, and then is subjected to Click reaction with 3-azidopropyl heptaphenyl POSS, so that the silsesquioxane-terminated star-shaped hyperbranched polyester is obtained.
The specific operation is as follows:
(1) Synthetic castor oil-based hyperbranched polyol: the molar ratio is 1:3 (18.33 g,0.01 mol) and 2, 2-dimethylolpropionic acid (8.02 g,0.03 mol) as raw materials, p-toluene sulfonic acid (0.03 g) as a catalyst. After dissolving 2, 2-dimethylolpropionic acid in xylene, it was placed in a three-necked round bottom flask equipped with a mechanical stirrer, dean-Stark apparatus and nitrogen inlet. Then, after castor oil was slowly added for 10min, p-toluenesulfonic acid was added. After the completion of the addition, the reaction mixture was reacted under nitrogen at 180℃for three hours, during which time the reaction was stopped after the acid value reached 10mg KOH/g by detecting the pH every 30 minutes.
(2) Alkynyl-terminated castor oil-based hyperbranched polyol synthesis: castor oil-based hyperbranched polyol and propidium bromide react under the action of sodium hydride to prepare alkynyl-terminated castor oil-based hyperbranched polyol, 48g of NaH (20 mmol) is dissolved in 50mL of dry THF, poured into a 500mL single-neck glass flask, and placed in an ice-water bath. 1.1g of castor oil-based hyperbranched polyol was dissolved in 110mL of dry THF, added dropwise to the flask with a constant pressure dropping funnel, and the reaction was continued for 3 hours after the completion of the addition. 2.379g of propargyl bromide (20: 20 mmoL) was dissolved in 10mL of dry THF, and the mixture was added dropwise to the reaction system via a constant pressure dropping funnel, followed by reaction at room temperature for 24 hours after the completion of the addition. After filtration, a part of the solvent was removed by a rotary evaporator, and then precipitated with petroleum ether to remove the salt (NaBr) formed in the reaction system and the excess NaH during the reaction. Vacuum filtering, drying in vacuum oven at 30deg.C, dissolving with appropriate amount of THF, washing with petroleum ether to obtain unreacted micromolecular substance, precipitating to obtain crude product, repeating operation for 3 times, and drying again to obtain pure alkynyl-terminated castor oil-based hyperbranched polyol product.
(3) Synthesis of heptaphenyl trisilanols sodium salt: heptaphenyl trisilanolsodium salt is a necessary precursor for synthesizing phenyl POSS, 54.648g of phenyl trimethoxysilane (276.0 mmol) is dissolved in 300ml of THF, placed in a dry 500ml flask, and 6.31g of deionized water (350.64 mmol) and 4.75g of sodium hydroxide (118.8 mmol) are added. The flask containing the mixture was placed in an oil bath at 70℃and reacted at reflux for 5 hours, after which the oil bath was turned off and the reaction was continued for 15 hours. The volatile components of the flask were removed by rotary evaporation, such as THF. And then placing the obtained white solid in a baking oven at 40 ℃ for vacuum drying for 24 hours, thus obtaining the heptaphenyl trisilanol sodium salt product.
(4) Synthesis of bromopropyl heptaphenyl POSS: is synthesized by adopting a top angle-cap reaction of heptaphenyl trisilanolsodium salt [ Na 3OSi(C6H5)7 ] and trichlorosilane. 36.09g of heptaphenylsilanol sodium salt [ Na 3OSi(C6H5)7 ] (36.24 mmol) was dissolved in 400mL of a dry and treated THF solution, placed in a flask and rapidly capped with a rubber stopper, the temperature of the reaction system was lowered to below 0℃in an ice-water bath, 13.37g of 3-bromopropyl trichlorosilane (52.25 mmol) was added with rapid stirring, the above reaction was continued at 0℃for 3 hours, and the above reaction was continued at room temperature for 15 hours. After filtration, part of the solvent was removed by a rotary evaporator, and the crude product was precipitated with frozen methanol, and after 3 repeated operations, the reaction product was recrystallized in a petroleum ether/THF (volume ratio=1:2) solution, and then dried in a vacuum oven at 40 ℃ for 24 hours to obtain a pure bromopropyl heptaphenyl POSS chemical reaction product.
(5) Synthesis of 3-azidopropyl heptaphenyl POSS: the bromopropyl heptaphenyl POSS and sodium azide are subjected to nucleophilic substitution reaction, 3.97g of bromopropyl heptaphenyl POSS (3 mmol) and 0.195g of NaN 3 (4 mmol) are dissolved in 6mL of THF/DMF, after reaction for 24 hours at 30 ℃, solid-liquid separation is carried out by vacuum filtration, a rotary evaporation instrument is used for volatilizing the solvent, the residue is washed by 5mL of deionized water, and the obtained product is placed in a 40 ℃ oven for vacuum drying for 24 hours, thus obtaining the 3-azidopropyl heptaphenyl POSS product.
(6) Synthesis of silsesquioxane-terminated star-shaped hyperbranched polyester: the preparation method is characterized in that the preparation method comprises the steps of carrying out Click reaction on alkynyl-terminated castor oil-based hyperbranched polyol and 3-azidopropyl heptaphenyl POSS. Into a 50mL single-necked glass flask, 0.255g of an alkynyl-terminated castor oil-based hyperbranched polyol (0.19 mmol), 1.33g of azido heptaphenyl POSS (1.28 mmol) were successively added, and 32mL of THF was added to dissolve it sufficiently. The reaction system was continuously purged with high purity nitrogen for 45 minutes, followed by the sequential addition of 6mg of cuprous bromide (CuBr) and 8.56. Mu.L of Polyamine (PMDETA). The reaction system was reacted at room temperature 24℃for 24 hours. After the reaction is finished, the rubber plug is opened, so that the atmosphere enters the reaction vessel to terminate the reaction. Part of the solvent was removed by rotary evaporator, then precipitated in petroleum ether, and freeze-dried in an oven at 40℃for 24 hours to obtain a reaction product.
The polycarbonate modified plastic for limiting the ambient temperature is prepared by a method comprising the following steps:
(1) Weighing the components;
(2) Respectively drying the siloxane copolycarbonate resin and the polycarbonate at 130 ℃ for 4 hours, drying other components at 80 ℃ for 2 hours, and fully mixing the components according to a proportion for 3-5 minutes;
(3) And (3) putting the mixed materials into a double-screw extruder for extrusion granulation, and controlling the rotating speed of a screw to be 200-500 rpm to obtain the polycarbonate modified plastic.
In the method, the double-screw extruder comprises 9 temperature control areas, wherein the temperature of the temperature control area 1 is 230-250 ℃, the temperature of the temperature control area 2 is 240-260 ℃, the temperature of the temperature control area 3-5 is 250-270 ℃, the temperature of the temperature control area 6 is 240-260 ℃, and the temperature of the temperature control area 7-9 is 240-260 ℃; the rotating speed of the host machine is 280-360 rpm; the grain cutting speed is 300-420 rpm;
Preferably, the double-screw extruder is provided with two vacuumizing positions, one position is positioned at the joint of the tail end of the material conveying section and the beginning end of the melting section, and the other position is positioned at the metering section.
Compared with the prior art, the invention has the advantages that:
The invention utilizes specific siloxane copolycarbonate resin and specific polycarbonate to compound in a specific mass ratio, and improves the low-temperature resistance and shock resistance of the polycarbonate composite material by increasing the free volume of a molecular chain in a system and improving the compatibility with the siloxane copolycarbonate resin and the polycarbonate in the system after the silsesquioxane-terminated star-shaped hyperbranched polyester additive is added; the prepared polycarbonate composite material is particularly suitable for plastic products at extreme ambient temperature, such as shells of interphones, shells of anti-riot clothing and the like.
Detailed Description
The following detailed description of the invention is provided in connection with the accompanying drawings that are presented to illustrate the invention and not to limit the scope thereof. The examples provided below are intended as guidelines for further modifications by one of ordinary skill in the art and are not to be construed as limiting the invention in any way.
The experimental methods in the following examples, unless otherwise specified, are conventional methods, and are carried out according to techniques or conditions described in the literature in the field or according to the product specifications. Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
The silsesquioxane-terminated star hyperbranched polyester in the following examples is prepared by the following method:
(1) Synthetic castor oil-based hyperbranched polyol: the molar ratio is 1:3 (18.33 g,0.01 mol) and 2, 2-dimethylolpropionic acid (8.02 g,0.03 mol) as raw materials, p-toluene sulfonic acid (0.03 g) as a catalyst. After dissolving 2, 2-dimethylolpropionic acid in xylene, it was placed in a three-necked round bottom flask equipped with a mechanical stirrer, dean-Stark apparatus and nitrogen inlet. Then, after castor oil was slowly added for 10min, p-toluenesulfonic acid was added. After the completion of the addition, the reaction mixture was reacted under nitrogen at 180℃for three hours, during which time the reaction was stopped after the acid value reached 10mg KOH/g by detecting the pH every 30 minutes.
(2) Alkynyl-terminated castor oil-based hyperbranched polyol synthesis: castor oil-based hyperbranched polyol and propidium bromide react under the action of sodium hydride to prepare alkynyl-terminated castor oil-based hyperbranched polyol, 48g of NaH (20 mmol) is dissolved in 50mL of dry THF, poured into a 500mL single-neck glass flask, and placed in an ice-water bath. 1.1g of castor oil-based hyperbranched polyol was dissolved in 110mL of dry THF, added dropwise to the flask with a constant pressure dropping funnel, and the reaction was continued for 3 hours after the completion of the addition. 2.379g of propargyl bromide (20: 20 mmoL) was dissolved in 10mL of dry THF, and the mixture was added dropwise to the reaction system via a constant pressure dropping funnel, followed by reaction at room temperature for 24 hours after the completion of the addition. After filtration, a part of the solvent was removed by a rotary evaporator, and then precipitated with petroleum ether to remove the salt (NaBr) formed in the reaction system and the excess NaH during the reaction. Vacuum filtering, drying in vacuum oven at 30deg.C, dissolving with appropriate amount of THF, washing with petroleum ether to obtain unreacted micromolecular substance, precipitating to obtain crude product, repeating operation for 3 times, and drying again to obtain pure alkynyl-terminated castor oil-based hyperbranched polyol product.
(3) Synthesis of heptaphenyl trisilanols sodium salt: heptaphenyl trisilanolsodium salt is a necessary precursor for synthesizing phenyl POSS, 54.648g of phenyl trimethoxysilane (276.0 mmol) is dissolved in 300ml of THF, placed in a dry 500ml flask, and 6.31g of deionized water (350.64 mmol) and 4.75g of sodium hydroxide (118.8 mmol) are added. The flask containing the mixture was placed in an oil bath at 70℃and reacted at reflux for 5 hours, after which the oil bath was turned off and the reaction was continued for 15 hours. The volatile components of the flask were removed by rotary evaporation, such as THF. And then placing the obtained white solid in a baking oven at 40 ℃ for vacuum drying for 24 hours, thus obtaining the heptaphenyl trisilanol sodium salt product.
(4) Synthesis of bromopropyl heptaphenyl POSS: is synthesized by adopting a top angle-cap reaction of heptaphenyl trisilanolsodium salt [ Na 3OSi(C6H5)7 ] and trichlorosilane. 36.09g of heptaphenylsilanol sodium salt [ Na 3OSi(C6H5)7 ] (36.24 mmol) was dissolved in 400mL of a dry and treated THF solution, placed in a flask and rapidly capped with a rubber stopper, the temperature of the reaction system was lowered to below 0℃in an ice-water bath, 13.37g of 3-bromopropyl trichlorosilane (52.25 mmol) was added with rapid stirring, the above reaction was continued at 0℃for 3 hours, and the above reaction was continued at room temperature for 15 hours. After filtration, part of the solvent was removed by a rotary evaporator, and the crude product was precipitated with frozen methanol, and after 3 repeated operations, the reaction product was recrystallized in a petroleum ether/THF (volume ratio=1:2) solution, and then dried in a vacuum oven at 40 ℃ for 24 hours to obtain a pure bromopropyl heptaphenyl POSS chemical reaction product.
(5) Synthesis of 3-azidopropyl heptaphenyl POSS: the bromopropyl heptaphenyl POSS and sodium azide are subjected to nucleophilic substitution reaction, 3.97g of bromopropyl heptaphenyl POSS (3 mmol) and 0.195g of NaN 3 (4 mmol) are dissolved in 6mL of THF/DMF, after reaction for 24 hours at 30 ℃, solid-liquid separation is carried out by vacuum filtration, a rotary evaporation instrument is used for volatilizing the solvent, the residue is washed by 5mL of deionized water, and the obtained product is placed in a 40 ℃ oven for vacuum drying for 24 hours, thus obtaining the 3-azidopropyl heptaphenyl POSS product.
(6) Synthesis of silsesquioxane-terminated star-shaped hyperbranched polyester: the preparation method is characterized in that the preparation method comprises the steps of carrying out Click reaction on alkynyl-terminated castor oil-based hyperbranched polyol and 3-azidopropyl heptaphenyl POSS. Into a 50mL single-necked glass flask, 0.255g of an alkynyl-terminated castor oil-based hyperbranched polyol (0.19 mmol), 1.33g of azido heptaphenyl POSS (1.28 mmol) were successively added, and 32mL of THF was added to dissolve it sufficiently. The reaction system was continuously purged with high purity nitrogen for 45 minutes, followed by the sequential addition of 6mg of cuprous bromide (CuBr) and 8.56. Mu.L of Polyamine (PMDETA). The reaction system was reacted at room temperature 24℃for 24 hours. After the reaction is finished, the rubber plug is opened, so that the atmosphere enters the reaction vessel to terminate the reaction. Part of the solvent was removed by rotary evaporator, then precipitated in petroleum ether, and freeze-dried in an oven at 40℃for 24 hours to obtain a reaction product.
Example 1 preparation of polycarbonate modified Plastic for extreme Environment temperature
The polycarbonate modified plastic is prepared from the following substances in percentage by weight: 38.4% of siloxane copolymerized polycarbonate resin, 57.6% of polycarbonate resin, 3% of silsesquioxane-terminated star hyperbranched polyester, 0.4% of flame retardant, 0.2% of antioxidant, 0.3% of light stabilizer and 0.1% of other auxiliary agents.
The siloxane copolymerized polycarbonate resin is prepared from bisphenol A and siloxane copolymerized polycarbonate resin, the commercial name is CH9115, the relative molecular weight is 24000, the average phase region size of a polysiloxane chain segment is 30-60 nm, and the mass melt flow rate is 9-12 g/10min at 300 ℃/1.2 kg;
the polycarbonate resin is A1105, purchased from Wanhua chemical company;
The antioxidant is a compound of antioxidant 168 and antioxidant 1010, and the weight ratio of the compound is 1:1, a step of;
The light stabilizer is a compound of UV981 and UV-329, and the compound weight ratio is 1:1, a step of;
the flame retardant was PX-200, available from Daba chemical Japan.
The other auxiliary agents are black master batches.
The preparation method comprises the following steps:
drying the siloxane copolycarbonate resin and the polycarbonate resin for 4 hours at 130 ℃, drying the auxiliary agent for 2 hours at 80 ℃, and fully mixing for 5 minutes according to a proportion;
And (3) putting the mixed materials into a double-screw extruder for extrusion granulation, and controlling the rotating speed of the screw to be 200-500 rpm.
The double-screw extruder comprises 9 temperature control areas, wherein the temperature of the temperature control area 1 is 230-250 ℃, the temperature of the temperature control area 2 is 240-260 ℃, the temperature of the temperature control area 3-5 is 250-270 ℃, the temperature of the temperature control area 6 is 240-260 ℃, and the temperature of the temperature control area 7-9 is 240-260 ℃; the rotating speed of the host machine is 280-360 rpm; the dicing speed is 300-420 rpm.
Example 2 preparation of polycarbonate modified Plastic for extreme Environment temperature
The polycarbonate modified plastic is prepared from the following substances in percentage by weight: 43.2% of siloxane copolycarbonate resin, 52.8% of polycarbonate resin, 3% of silsesquioxane-terminated star hyperbranched polyester, 0.4% of flame retardant, 0.2% of antioxidant, 0.3% of light stabilizer and 0.1% of other auxiliary agents.
The siloxane copolymerized polycarbonate resin is prepared from bisphenol A and siloxane copolymerized polycarbonate resin, the commercial name is CH9115, the relative molecular weight is 24000, the average phase region size of a polysiloxane chain segment is 30-60 nm, and the mass melt flow rate is 9-12 g/10min at 300 ℃/1.2 kg;
the polycarbonate resin is A1105, purchased from Wanhua chemical company;
The antioxidant is a compound of antioxidant 168 and antioxidant 1010, and the weight ratio of the compound is 1:1, a step of;
The light stabilizer is a compound of UV981 and UV-329, and the compound weight ratio is 1:1, a step of;
The flame retardant is PX-200, available from Dagaku chemical Japan;
The other auxiliary agents are black master batches.
The preparation method comprises the following steps:
drying the siloxane copolycarbonate resin and the polycarbonate resin for 4 hours at 130 ℃, drying the auxiliary agent for 2 hours at 80 ℃, and fully mixing for 5 minutes according to a proportion;
And (3) putting the mixed materials into a double-screw extruder for extrusion granulation, and controlling the rotating speed of the screw to be 200-500 rpm.
The double-screw extruder comprises 9 temperature control areas, wherein the temperature of the temperature control area 1 is 230-250 ℃, the temperature of the temperature control area 2 is 240-260 ℃, the temperature of the temperature control area 3-5 is 250-270 ℃, the temperature of the temperature control area 6 is 240-260 ℃, and the temperature of the temperature control area 7-9 is 240-260 ℃; the rotating speed of the host machine is 280-360 rpm; the dicing speed is 300-420 rpm.
Example 3 preparation of polycarbonate modified Plastic for extreme Environment temperature
The polycarbonate modified plastic is prepared from the following substances in percentage by weight: 48% of siloxane copolymerized polycarbonate resin, 48% of polycarbonate resin, 3% of silsesquioxane-terminated star hyperbranched polyester, 0.4% of flame retardant, 0.2% of antioxidant, 0.3% of light stabilizer and 0.1% of other auxiliary agents.
The siloxane copolymerized polycarbonate resin is prepared from bisphenol A and siloxane copolymerized polycarbonate resin, the commercial name is CH9115, the relative molecular weight is 24000, the average phase region size of a polysiloxane chain segment is 30-60 nm, and the mass melt flow rate is 9-12 g/10min at 300 ℃/1.2 kg;
the polycarbonate resin is A1105, purchased from Wanhua chemical company;
The antioxidant is a compound of antioxidant 168 and antioxidant 1010, and the weight ratio of the compound is 1:1, a step of;
The light stabilizer is a compound of UV981 and UV-329, and the compound weight ratio is 1:1, a step of;
The flame retardant is PX-200, available from Dagaku chemical Japan;
The other auxiliary agents are black master batches.
The preparation method comprises the following steps:
drying the siloxane copolycarbonate resin and the polycarbonate resin for 4 hours at 130 ℃, drying the auxiliary agent for 2 hours at 80 ℃, and fully mixing for 5 minutes according to a proportion;
And (3) putting the mixed materials into a double-screw extruder for extrusion granulation, and controlling the rotating speed of the screw to be 200-500 rpm.
The double-screw extruder comprises 9 temperature control areas, wherein the temperature of the temperature control area 1 is 230-250 ℃, the temperature of the temperature control area 2 is 240-260 ℃, the temperature of the temperature control area 3-5 is 250-270 ℃, the temperature of the temperature control area 6 is 240-260 ℃, and the temperature of the temperature control area 7-9 is 240-260 ℃; the rotating speed of the host machine is 280-360 rpm; the dicing speed is 300-420 rpm.
Example 4 preparation of polycarbonate modified Plastic for extreme Environment temperature
The polycarbonate modified plastic is prepared from the following substances in percentage by weight: 52.8% of siloxane copolymerized polycarbonate resin, 43.2% of polycarbonate resin, 3% of silsesquioxane-terminated star hyperbranched polyester, 0.4% of flame retardant, 0.2% of antioxidant, 0.3% of light stabilizer and 0.1% of other auxiliary agents.
The siloxane copolymerized polycarbonate resin is prepared from bisphenol A and siloxane copolymerized polycarbonate resin, the commercial name is CH9115, the relative molecular weight is 24000, the average phase region size of a polysiloxane chain segment is 30-60 nm, and the mass melt flow rate is 9-12 g/10min at 300 ℃/1.2 kg;
the polycarbonate resin is A1105, purchased from Wanhua chemical company;
The antioxidant is a compound of antioxidant 168 and antioxidant 1010, and the weight ratio of the compound is 1:1, a step of;
The light stabilizer is a compound of UV981 and UV-329, and the compound weight ratio is 1:1, a step of;
The flame retardant is PX-200, available from Dagaku chemical Japan;
The other auxiliary agents are black master batches.
The preparation method comprises the following steps:
drying the siloxane copolycarbonate resin and the polycarbonate resin for 4 hours at 130 ℃, drying the auxiliary agent for 2 hours at 80 ℃, and fully mixing for 5 minutes according to a proportion;
And (3) putting the mixed materials into a double-screw extruder for extrusion granulation, and controlling the rotating speed of the screw to be 200-500 rpm.
The double-screw extruder comprises 9 temperature control areas, wherein the temperature of the temperature control area 1 is 230-250 ℃, the temperature of the temperature control area 2 is 240-260 ℃, the temperature of the temperature control area 3-5 is 250-270 ℃, the temperature of the temperature control area 6 is 240-260 ℃, and the temperature of the temperature control area 7-9 is 240-260 ℃; the rotating speed of the host machine is 280-360 rpm; the dicing speed is 300-420 rpm.
Example 5 preparation of polycarbonate modified Plastic for extreme Environment temperature
The polycarbonate modified plastic is prepared from the following substances in percentage by weight: 57.6% of siloxane copolymerized polycarbonate resin, 38.4% of polycarbonate resin, 3% of silsesquioxane-terminated star hyperbranched polyester, 0.4% of flame retardant, 0.2% of antioxidant, 0.3% of light stabilizer and 0.1% of other auxiliary agents.
The siloxane copolymerized polycarbonate resin is prepared from bisphenol A and siloxane copolymerized polycarbonate resin, the commercial name is CH9115, the relative molecular weight is 24000, the average phase region size of a polysiloxane chain segment is 30-60 nm, and the mass melt flow rate is 9-12 g/10min at 300 ℃/1.2 kg;
the polycarbonate resin is A1105, purchased from Wanhua chemical company;
The antioxidant is a compound of antioxidant 168 and antioxidant 1010, and the weight ratio of the compound is 1:1, a step of;
The light stabilizer is a compound of UV981 and UV-329, and the compound weight ratio is 1:1, a step of;
The flame retardant is PX-200, available from Dagaku chemical Japan;
The other auxiliary agents are black master batches.
The preparation method comprises the following steps:
drying the siloxane copolycarbonate resin and the polycarbonate resin for 4 hours at 130 ℃, drying the auxiliary agent for 2 hours at 80 ℃, and fully mixing for 5 minutes according to a proportion;
And (3) putting the mixed materials into a double-screw extruder for extrusion granulation, and controlling the rotating speed of the screw to be 200-500 rpm.
The double-screw extruder comprises 9 temperature control areas, wherein the temperature of the temperature control area 1 is 230-250 ℃, the temperature of the temperature control area 2 is 240-260 ℃, the temperature of the temperature control area 3-5 is 250-270 ℃, the temperature of the temperature control area 6 is 240-260 ℃, and the temperature of the temperature control area 7-9 is 240-260 ℃; the rotating speed of the host machine is 280-360 rpm; the dicing speed is 300-420 rpm.
Comparative example 1 preparation of polycarbonate modified Plastic
The difference compared to example 1 is that the siloxane copolycarbonate resin and the silsesquioxane-terminated star hyperbranched polyester were not added, the polycarbonate resin was 99%, and the other conditions were unchanged.
Comparative example 2 preparation of polycarbonate modified Plastic
The difference compared to example 1 is that the double-half siloxane-terminated star-shaped hyperbranched polyester was not added, the siloxane copolymerized polycarbonate resin was 39.6%, the polycarbonate resin was 59.4%, and the other conditions were unchanged.
Comparative example 3 preparation of polycarbonate modified Plastic
The difference compared to example 1 is that the double-half siloxane-terminated star-shaped hyperbranched polyester was not added, the siloxane copolymerized polycarbonate resin 44.55%, the polycarbonate resin 54.45% and the other conditions were unchanged.
Comparative example 4 preparation of polycarbonate modified Plastic
The difference compared to example 1 is that the double-half siloxane-terminated star-shaped hyperbranched polyester was not added, the siloxane copolymerized polycarbonate resin was 49.5%, the polycarbonate resin was 49.5%, and the other conditions were unchanged.
Comparative example 5 preparation of polycarbonate modified Plastic
The difference compared to example 1 is that the double-half siloxane-terminated star-shaped hyperbranched polyester was not added, the siloxane copolymerized polycarbonate resin was 54.45%, the polycarbonate resin was 44.55%, and the other conditions were unchanged.
Comparative example 6 preparation of polycarbonate modified Plastic
The difference compared to example 1 is that the double-half siloxane-terminated star-shaped hyperbranched polyester, the siloxane copolycarbonate resin 59.4%, the polycarbonate resin 39.6% and the other conditions were unchanged.
Comparative example 7 preparation of polycarbonate Plastic
The difference compared to example 1 is that the double-half siloxane-terminated star-like hyperbranched polyester and polycarbonate resin were not added, the siloxane copolycarbonate resin was 99%, and the other conditions were unchanged.
Table 1: examples 1 to 5 and comparative examples 1 to 7 compositions of polycarbonate-modified plastics for extreme environmental temperatures
Results of various properties of the obtained product
Table 2: examples 1 to 5 preparation of polycarbonate-modified plastics for extreme ambient temperatures and comparison of Properties of the products prepared in comparative examples 1 to 7
Compared with the prior art, the invention has the following advantages:
Based on the above, the invention adopts the specific siloxane copolycarbonate resin and the specific polycarbonate to compound according to the specific mass ratio, and after the silsesquioxane end-capped star-shaped hyperbranched polyester additive is added, the low-temperature shock resistance of the polycarbonate composite material is improved by enlarging the free volume of molecular chain movement in the system, improving the compatibility with the siloxane copolycarbonate resin and the polycarbonate in the system, reducing the interfacial tension.
The present application is described in detail above. It will be apparent to those skilled in the art that the present application can be practiced in a wide range of equivalent parameters, concentrations, and conditions without departing from the spirit and scope of the application and without undue experimentation. While the application has been described with respect to specific embodiments, it will be appreciated that the application may be further modified. In general, this application is intended to cover any variations, uses, or adaptations of the application following, in general, the principles of the application and including such departures from the present disclosure as come within known or customary practice within the art to which the application pertains.
Claims (5)
1. The polycarbonate modified plastic for limiting ambient temperature is prepared from the following components in parts by weight:
38-58% of siloxane copolymerized polycarbonate resin, 38-58% of polycarbonate resin, 2-4% of silsesquioxane end-capped star hyperbranched polyester, 0.1-1% of flame retardant, 0.01-1% of antioxidant, 0.01-1% of light stabilizer and 0.01-1% of other auxiliary agents;
wherein the silicone copolycarbonate resin is CH9115, available from the company of large, cangzhou;
the polycarbonate resin is A1105, purchased from Wanhua chemical company;
the structural formula of the silsesquioxane-terminated star-shaped hyperbranched polyester is as follows:
Wherein,
2. The polycarbonate-modified plastic of claim 1, wherein: the flame retardant is at least one of polysilaborane flame retardant and phenylene phosphate flame retardant; the antioxidant is at least one of acrylic acid ester antioxidants and phosphite ester antioxidants; the light stabilizer is one or a mixture of UV234, UV981, UV-329 and UV-360; the other auxiliary agents are black master batches.
3. The polycarbonate-modified plastic according to claim 1 or 2, characterized in that: the antioxidant is a compound of antioxidant 168 and antioxidant 1010, and the weight ratio of the compound is 1:1, a step of;
The light stabilizer is a compound of UV981 and UV-329, and the compound weight ratio is 1:1, a step of;
the flame retardant is PX-200.
4. A method of preparing the polycarbonate-modified plastic of any of claims 1-3, comprising the steps of:
(1) Weighing the components;
(2) Respectively drying the siloxane copolycarbonate resin and the polycarbonate at 130 ℃ for 4 hours, drying other components at 80 ℃ for 2 hours, and fully mixing the components according to a proportion for 3-5 minutes;
(3) And (3) putting the mixed materials into a double-screw extruder for extrusion granulation, and controlling the rotating speed of a screw to be 200-500 rpm to obtain the polycarbonate modified plastic.
5. The method according to claim 4, wherein: the double-screw extruder comprises 9 temperature control areas, wherein the temperature of the temperature control area 1 is 230-250 ℃, the temperature of the temperature control area 2 is 240-260 ℃, the temperature of the temperature control area 3-5 is 250-270 ℃, the temperature of the temperature control area 6 is 240-260 ℃, and the temperature of the temperature control area 7-9 is 240-260 ℃; the rotating speed of the host machine is 280-360 rpm; the dicing speed is 300-420 rpm.
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| EP1616557A2 (en) * | 2004-07-16 | 2006-01-18 | L'oreal | Cosmetic composition containing a selected silicone polymer and a film-forming agent |
| CN101250375A (en) * | 2008-04-03 | 2008-08-27 | 同济大学 | POSS/polyurethane aqueous composite paint and preparation method thereof |
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