CN117343330A - Phenyl silicone resin containing branched structure and preparation method and application thereof - Google Patents
Phenyl silicone resin containing branched structure and preparation method and application thereof Download PDFInfo
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 title claims abstract description 34
- 229920002050 silicone resin Polymers 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 229920005989 resin Polymers 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 27
- 125000003944 tolyl group Chemical group 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- 150000002081 enamines Chemical class 0.000 claims abstract description 11
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 10
- 239000010948 rhodium Substances 0.000 claims abstract description 10
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 238000007259 addition reaction Methods 0.000 claims abstract description 6
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006482 condensation reaction Methods 0.000 claims abstract description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000003377 acid catalyst Substances 0.000 claims description 10
- ASVKKRLMJCWVQF-UHFFFAOYSA-N 3-buten-1-amine Chemical compound NCCC=C ASVKKRLMJCWVQF-UHFFFAOYSA-N 0.000 claims description 9
- 238000006386 neutralization reaction Methods 0.000 claims description 9
- -1 rhodium (I) 2-ethylhexanoate Chemical compound 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 150000003384 small molecules Chemical class 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 claims description 6
- FICBXRYQMBKLJJ-UHFFFAOYSA-N hex-5-en-1-amine Chemical compound NCCCCC=C FICBXRYQMBKLJJ-UHFFFAOYSA-N 0.000 claims description 5
- UVBBCQLPTZEDHT-UHFFFAOYSA-N pent-4-en-1-amine Chemical compound NCCCC=C UVBBCQLPTZEDHT-UHFFFAOYSA-N 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- HAURRGANAANPSQ-UHFFFAOYSA-N cis-2,4,6-Trimethyl-2,4,6-triphenylcyclotrisiloxane Chemical compound O1[Si](C)(C=2C=CC=CC=2)O[Si](C)(C=2C=CC=CC=2)O[Si]1(C)C1=CC=CC=C1 HAURRGANAANPSQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005538 encapsulation Methods 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Substances C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 2
- IRVZFACCNZRHSJ-UHFFFAOYSA-N 2,4,6,8-tetramethyl-2,4,6,8-tetraphenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound O1[Si](C)(C=2C=CC=CC=2)O[Si](C)(C=2C=CC=CC=2)O[Si](C)(C=2C=CC=CC=2)O[Si]1(C)C1=CC=CC=C1 IRVZFACCNZRHSJ-UHFFFAOYSA-N 0.000 claims 1
- AMLFJZRZIOZGPW-UHFFFAOYSA-N prop-1-en-1-amine Chemical compound CC=CN AMLFJZRZIOZGPW-UHFFFAOYSA-N 0.000 claims 1
- 238000005452 bending Methods 0.000 abstract description 6
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 238000004806 packaging method and process Methods 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 239000005022 packaging material Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- 239000001257 hydrogen Chemical group 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- BNKAXGCRDYRABM-UHFFFAOYSA-N ethenyl dihydrogen phosphate Chemical compound OP(O)(=O)OC=C BNKAXGCRDYRABM-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920002545 silicone oil Polymers 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229910002808 Si–O–Si Chemical group 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- CMYSYMOUPIMLDF-UHFFFAOYSA-N 6,6,6-trifluorohexane-1-sulfonic acid Chemical compound FC(CCCCCS(=O)(=O)O)(F)F CMYSYMOUPIMLDF-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- KYEXLJGCLGSPTJ-UHFFFAOYSA-N C1=CC=CC2=CC=C3C=C4C(=CC=CC4=CC3=C12)[SiH]1O[SiH2]O[SiH2]O1 Chemical compound C1=CC=CC2=CC=C3C=C4C(=CC=CC4=CC3=C12)[SiH]1O[SiH2]O[SiH2]O1 KYEXLJGCLGSPTJ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- IXAYKDDZKIZSPV-UHFFFAOYSA-M [Rh]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 Chemical compound [Rh]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 IXAYKDDZKIZSPV-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- XJWOWXZSFTXJEX-UHFFFAOYSA-N phenylsilicon Chemical compound [Si]C1=CC=CC=C1 XJWOWXZSFTXJEX-UHFFFAOYSA-N 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/395—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/58—Optical field-shaping elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Silicon Polymers (AREA)
Abstract
The invention provides phenyl silicone resin containing a branched structure, and a preparation method and application thereof. The resin structure is
Description
Technical Field
The invention belongs to the field of phenyl silicone resin, and particularly relates to phenyl silicone resin containing a branched structure, and a preparation method and application thereof.
Background
The high refractive index LED packaging material is mainly phenyl type organic silicon material because the benzene ring has higher molar refractive index and relatively smaller molecular volume. The larger the mass fraction of phenyl groups, the higher the refractive index and the lower the shrinkage of the material. However, because the phenyl has larger rigidity and larger steric hindrance, the molecular movement is limited when the phenyl is impacted by stress, and the shock resistance and the tensile resistance are poor, other groups are required to be introduced to strengthen the absorption of the resin to the stress, so that the shock resistance, the tensile resistance and the bending resistance of the resin are improved, and the application performance of the resin in the flexible LED packaging material is improved.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide phenyl silicone resin containing a branched structure. The resin improves the impact resistance, tensile resistance and bending resistance of the resin, so that the resin can be applied to flexible LED packaging materials.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a phenyl silicone resin having a branched structure, said resin having a structure represented by formula 1:
wherein n is an integer of 1 or more, preferably n is 10 to 40, m is an integer of 1 or more, preferably m is 3 to 6.
The invention provides phenyl silicone resin containing a branched structure, wherein the molecular structure of the resin contains phenyl groups, so that the refractive index of the silicone resin can be improved, meanwhile, ionic bonds formed by phosphonic acid groups and amino groups, hydrogen bonds formed between O on phosphonic acid groups and H on amino groups and Si-O-Si bonds existing on a main chain of the resin exist in the structure, when the stress is relatively small, the ionic bonds and covalent bonds fracture and absorb energy, when the stress is relatively large, the impact resistance, tensile resistance and bending resistance of the silicone resin are improved, and the packaging material is endowed with excellent elastic recovery and stress absorption capacity, and the synthesis process is stable and feasible and suitable for industrial production.
It is another object of the present invention to provide a method for preparing phenyl silicone resins containing branched structures.
A process for preparing a phenyl silicone resin containing a branched structure, said resin being a resin as described above, said process comprising the steps of:
s1: the mixed ring of methyl phenyl siloxane and 1, 3-tetramethyl disiloxane are subjected to ring-opening polymerization reaction under the action of an acid catalyst, the acid catalyst is neutralized after the reaction, and unreacted small molecules are removed after filtering solids, so that a compound shown in a formula 3 is obtained:
wherein n is an integer not less than 1, preferably n is 10 to 40;
s2: carrying out addition reaction on a compound of formula 3 and enamine under the action of a rhodium catalyst, and removing unreacted small molecules to obtain a compound of formula 2:
wherein n is an integer not less than 1, preferably n is 10 to 40, m is an integer not less than 1, preferably m is 3 to 6;
s3: and (3) carrying out condensation reaction on the compound shown in the formula 2 and vinyl phosphonic acid, and removing unreacted micromolecules to obtain a target product shown in the formula 1.
In the invention, the methyl phenyl siloxane mixed ring body of S1 contains one or more of 2,4, 6-trimethyl-2, 4, 6-triphenyl cyclotrisiloxane, 2,4,6, 8-tetramethyl-2, 4,6, 8-tetraphenyl cyclotrisiloxane and 2,4,6,8, 10-pentamethyl-2, 4,6,8, 10-pentamphenyl cyclopentasiloxane; preferably, the mass ratio of the methyl phenyl siloxane mixed ring body to the 1, 3-tetramethyl disiloxane is (12.6-50.7): 1.
In the present invention, the reaction of S1 is carried out under an inert atmosphere.
In the invention, the acid catalyst S1 is fluorine-containing organic acid with 1-7 carbon atoms, preferably trifluoro methane sulfonic acid; preferably, the dosage of the acid catalyst is 1 to 5 per mill of the total mass of the mixed ring body of the methyl phenyl siloxane and the 1, 3-tetramethyl disiloxane.
In the invention, the reaction temperature of S1 is 60-80 ℃ and the reaction time is 3-4 h.
In the invention, the neutralization of S1 adopts carbonate, preferably carbonate is one or more of alkali metal carbonate, more preferably calcium carbonate; preferably, the carbonate is used in an amount of 3-5% of the total mass of the mixed ring body of the methyl phenyl siloxane and the 1, 3-tetramethyl disiloxane; preferably, the reaction time of the carbonate neutralization acid catalyst is 1 to 2 hours.
In the invention, a short-range evaporator is adopted for devolatilizing and removing unreacted micromolecules in S1; preferably, the temperature for removing unreacted small molecules is 100-120 ℃ and the pressure is 0.1 KPaA-1 KPaA.
In the invention, the enamine of S2 is one or more of C3-C6 enamine, preferably acrylamide, 3-butene-1-amine, 4-pentene-1-amine and 5-hexene-1-amine, more preferably 3-butene-1-amine; preferably, the molar ratio of the compound of formula 3 to enamine is 1 (2-2.4).
In the present invention, the reaction of S2 is performed under an inert atmosphere.
In the invention, the rhodium catalyst in S2 is one or more of tris (triphenylphosphine) rhodium (I) chloride, triphenylphosphine acetylacetonato rhodium (I) carbonyl and rhodium (I) 2-ethylhexanoate; preferably, the rhodium catalyst is used in an amount of 1 to 5ppm based on the total mass of the compound of formula 3 and enamine, calculated as rhodium.
In the invention, the reaction temperature of S2 is 40-60 ℃ and the reaction time is 2-4 h.
In the invention, the temperature for removing unreacted micromolecules is 60-80 ℃ and the pressure is 0.1 KPaA-1 KPaA.
In the present invention, the molar ratio of the compound of formula 2 to vinylphosphonic acid (2 to 2.5) of S3 is 1.
In the invention, the reaction temperature of S3 is 80-100 ℃ and the reaction time is 8-10 h.
In the invention, the temperature for removing unreacted micromolecules is 100-120 ℃ and the pressure is 0.1 KPaA-1 KPaA.
It is a further object of the present invention to provide the use of phenyl silicone resins containing branched structures
Use of a phenyl silicone resin containing a branched structure, said resin being a resin as described above, or a resin prepared by a method as described above, for encapsulation of a high refractive index flexible LED.
In one embodiment, the phenyl silicone resin containing the branched structure is used as a raw material to prepare the high refractive index flexible LED packaging material. Specifically, the high refractive index flexible LED packaging material is prepared by the following method: a high refractive index flexible LED packaging material comprises an A component and a B component, wherein the A component comprises phenyl silicone resin containing a branched structure and a rhodium catalyst; the component B comprises phenyl silicone resin containing a branched structure, phenyl hydrogen-containing silicone oil and an inhibitor; specifically, the inhibitor may be ethynyl cyclohexanol, and the phenyl hydrogen-containing silicone oil may have a viscosity of 1800-2200cP.
Compared with the prior art, the invention has the following positive effects:
1) The cured glass has refractive index of more than 1.56 and high light transmittance of more than 98 percent;
2) The system contains ionic bonds formed by phosphonic acid groups and amino groups, hydrogen bonds formed between O on phosphonic acid groups and H on amino groups, and Si-O-Si bonds existing in a resin main chain, so that the hydrogen bonds are broken and absorb energy when small stress is applied, and the ionic bonds and covalent bonds are broken and absorb energy when large stress is applied, so that the packaging material has impact resistance, tensile resistance and bending resistance, and has excellent elastic recovery and stress absorption capacity.
Drawings
FIG. 1 shows the hydrogen nuclear magnetic resonance spectrum of phenyl silicone resin of example 1 1 H NMR)；
FIG. 2 shows nuclear magnetic resonance spectrum of phenyl silicone resin of example 1 13 C NMR)。
Detailed Description
The invention will now be further illustrated by means of specific examples which are given solely by way of illustration of the invention and do not limit the scope thereof.
The main raw material sources are as follows:
methyl phenyl siloxane mixed ring: sisburgh organosilicon PC9181 and methyl phenyl cyclosiloxane mixture comprises a tricyclic body, a tetracyclic body and a pentacyclic body, wherein the total effective components are more than 98.5%, and CAS number 68037-54-7;
1, 3-tetramethyldisiloxane: the purity of the Mongolian morning photochemical company is more than 99 percent, and the CAS number is 3277-26-7;
trifluoromethanesulfonic acid, trifluoromethanesulfonic acid: the purity of Jiangxi national industry Co.Ltd is more than 99.5 percent;
3-buten-1-amine: zhengzhou kepren biotechnology limited, purity > 95%, CAS No. 2524-49-4;
4-penten-1-amine: shanghai Tebert chemical technology Co., ltd., purity > 95%, CAS number 22537-07-1;
5-hexen-1-amine: nanjing Kang Man forest chemical industry Co., ltd., purity > 95%, CAS number 34825-70-2;
rhodium (I) tris (triphenylphosphine) chloride, rhodium (I) triphenylphosphine acetylacetonato carbonyl, rhodium (I) 2-ethylhexanoate: shaanxi Ruike New Material Co., ltd, purity > 99%;
vinyl phosphoric acid: hedrei (Shanghai) New Material Co., ltd., purity > 97%, CAS number 1746-03-8;
phenyl hydrogen silicone oil: viscosity 2000cP, believed chemical industry Co;
ethynyl cyclohexanol: sichuan Yibin Hengde chemical Co., ltd., purity > 99%, CAS number 78-27-3;
calcium carbonate, potassium carbonate, magnesium carbonate, sodium bicarbonate, sodium carbonate, aladine, analytically pure.
Other materials and reagents are commercially available without specific reference thereto.
The refractive index is tested according to national standard GB/T6488-2008, and the testing instrument is an ATAGO high refractive index Abbe refractometer NAR-4T;
the light transmittance is tested according to national standard GB/T2410-2008, and the testing instrument is a color spectrum light transmittance haze meter TH-100;
the tensile property is tested according to national standard GB/T2568-1995, and the testing instrument is Rongjia electronic tensile tester WDW-50S;
the tensile shear performance is tested according to national standard GB/T7124-2008, and the testing instrument is Rongjia electronic tensile tester WDW-50S;
the impact resistance is tested according to national standard GB/T1732-and the testing instrument is a Beijing pavilion instrument paint film impactor QCJ.
Example 1
Taking 5000ml four-port bottle, condensing and refluxing, protecting nitrogen, adding 4086g of methylphenyl ring, 324.3g of 1, 3-tetramethyl disiloxane and 4.41g of trifluoro methane sulfonic acid into a reaction kettle, heating to 60 ℃ for equilibrium reaction for 3 hours, adding 132.3g of calcium carbonate into the reaction kettle after the reaction is finished, stirring for neutralization for 2 hours, filtering to remove solids, taking filtrate, devolatilizing by a short-range evaporator, devolatilizing at 0.1KPaA and 120 ℃ to remove unreacted micromolecules, cooling the system to 40 ℃, adding 74.9g of 3-butene-1-amine into the system, heating to 60 ℃ after 0.0189g of tris (triphenylphosphine) rhodium (I) chloride, carrying out addition reaction for 2 hours, distilling to remove unreacted micromolecules at 0.1KPaA and 80 ℃ under negative pressure, adding 42.23g of vinyl phosphoric acid into the system, condensing at 80 ℃ for 10 hours, removing unreacted micromolecules at 0.1KPaA and 120 ℃ under negative pressure after the reaction is finished, and distilling to obtain the silicon-containing branched structure of the silicon resin shown by the unreacted micromolecule. The characterization results are shown in fig. 1 and 2.
Example 2
Taking 5000ml four-port bottle, condensing and refluxing, protecting nitrogen, adding 4086g of methylphenyl ring, 324.3g of 1, 3-tetramethyl disiloxane and 13.23g of trifluoro methane sulfonic acid into a reaction kettle, heating to 60 ℃ for equilibrium reaction for 3 hours, adding 176.5g of potassium carbonate into the reaction kettle after the reaction is finished, stirring for neutralization for 2 hours, filtering to remove solids, taking filtrate, devolatilizing by a short-range evaporator, devolatilizing at 0.5KPaA and 100 ℃ to remove unreacted micromolecules, cooling the system to 40 ℃, adding 89.7g of 4-pentene-1-amine into the system, adding 0.0190g of tris (triphenylphosphine) rhodium (I) chloride, heating to 60 ℃ for addition reaction for 2 hours, distilling to remove unreacted micromolecules at 0.1KPaA and 80 ℃ under negative pressure after the reaction is finished, adding 42.23g of vinyl phosphoric acid into the system, condensing at 80 ℃ for 10 hours, removing unreacted micromolecules at 0.1KPaA and 120 ℃ after the reaction is finished, and distilling to obtain the silicon-containing branched structure of the unreacted micromolecule 1 shown by the silicon.
Example 3
Taking 5000ml four-port bottle, condensing and refluxing, protecting nitrogen, adding 4086g of methylphenyl ring, 324.3g of 1, 3-tetramethyl disiloxane and 22.05g of trifluoro methane sulfonic acid into a reaction kettle, heating to 60 ℃ for equilibrium reaction for 4 hours, adding 220.5g of magnesium carbonate into the reaction kettle after the reaction is finished, stirring for neutralization for 2 hours, filtering to remove solids, taking filtrate, devolatilizing the filtrate by a short-range evaporator at 0.1KPaA and 120 ℃, cooling the system to 40 ℃, adding 74.9g of 5-hexene-1-amine into the system, heating to 60 ℃ for addition reaction for 4 hours, adding 42.23g of vinyl phosphoric acid into the system at the temperature of 60 ℃, condensing for 10 hours at the temperature of 80 ℃, removing unreacted micromolecules at the temperature of 0.1KPaA and 120 ℃ to obtain the phenyl silicon resin with a branched structure shown in the figure 1.
Example 4
Taking 5000ml four-port bottle, condensing and refluxing, protecting nitrogen, adding 4086g of methylphenyl ring, 160.8g of 1, 3-tetramethyl disiloxane and 4.25g of trifluoro-hexanesulfonic acid into a reaction kettle, heating to 60 ℃ for equilibrium reaction for 3 hours, adding 127.4g of sodium bicarbonate into the reaction kettle after the reaction is finished, stirring for neutralization for 2 hours, filtering to remove solids, taking filtrate, devolatilizing by a short-range evaporator at 0.1KPaA and 120 ℃ to remove unreacted micromolecules, cooling the system to 40 ℃, adding 34.7g of 3-butene-1-amine into the system, heating to 60 ℃ after 0.0184g of tris (triphenylphosphine) rhodium (I) chloride, distilling to remove unreacted micromolecules at 0.1KPaA and 80 ℃ after the reaction is finished, adding 16.89g of vinyl phosphoric acid into the system, condensing at 100 ℃ for 8 hours, distilling to remove unreacted micromolecules at 0.1KPaA and 100 ℃ after the reaction is finished, and obtaining the phenyl resin with a branched structure shown by the unreacted micromolecules.
Example 5
Taking 5000ml four-port bottle, condensing and refluxing, protecting nitrogen, adding 4086g of methylphenyl ring, 80.6g of 1, 3-tetramethyl disiloxane and 4.16g of trifluoromethanesulfonic acid into a reaction kettle, heating to 50 ℃ for equilibrium reaction for 3 hours, adding 125.0g of sodium carbonate into the reaction kettle after the reaction is finished, stirring for neutralization for 2 hours, filtering to remove solids, taking filtrate, devolatilizing by a short-range evaporator, devolatilizing at 0.1KPaA and 120 ℃ to remove unreacted micromolecules, cooling the system to 40 ℃, adding 93.6g of 3-butene-1-amine into the system, heating to 60 ℃ after adding 0.0194g of rhodium (I) 2-ethylhexanoate, distilling to remove unreacted micromolecules at 0.5KPaA and 80 ℃ after the reaction is finished, adding 63.3g of vinyl phosphoric acid into the system, condensing at 80 ℃ for 10 hours, removing unreacted micromolecules at 1KPaA and 120 ℃ after the reaction is finished, and distilling to obtain the phenyl resin with the branched structure shown in the formula 1.
Application example 1
The phenyl silicone resin containing the branched structure synthesized in the above example 1 is used as one of the formulation main agents of the flexible LED packaging material, and the flexible LED packaging material is prepared according to the following steps:
preparing a component A: 100g of phenyl silicone resin containing a branched structure is put into a 250ml reaction kettle to be stirred, the stirring speed is 300r/min, 0.1 part of catalyst tris (triphenylphosphine) rhodium (I) chloride is added, and the mixture is stirred for 30min in vacuum, so that the component A is obtained.
And (3) preparing a component B: 100g of phenyl silicone resin containing a branched structure, 30g of phenyl hydrogen-containing silicone oil and 0.01g of ethynyl cyclohexanol are sequentially put into a 250ml reaction kettle for stirring, the stirring speed is 1200r/min, vacuum is started to keep-0.1 MPa, and the vacuum stirring is carried out for 30min, so that the component B is obtained.
The A, B components are mixed and stirred for 5min at 250r/min and cured at room temperature. The prepared sample A1 is subjected to curing test on data such as refractive index, light transmittance, tensile property, tensile shear property, impact resistance and the like, and the test results are shown in Table 1.
Application examples 2 to 5
The flexible LED package materials were prepared according to the method in application example 1, respectively, except that the phenyl silicone resin containing a branched structure was used instead of examples 2 to 5, respectively, to prepare flexible LED package materials A2 to A5. The performance test in table 1 was also performed.
Comparative example 1
A flexible LED package material was prepared according to the method of application example 1, except that phenyl silicone resin containing a branched structure was replaced with commercially conventional linear phenyl vinyl silicone oil (Ai Yaoda silicone oil Co., ltd., IOTA 252), and a flexible LED package material D1 was prepared. The performance test in table 1 was also performed.
TABLE 1 Performance test results
| A1 | A2 | A3 | A4 | A5 | D1 | |
| Refractive index/% | 1.5840 | 1.5822 | 1.5803 | 1.5835 | 1.5843 | 1.5432 |
| Transmittance/% | 98.2 | 98.1 | 97.9 | 98.2 | 98.2 | 97.8 |
| Elongation at break/% | 10.8 | 10.3 | 10.5 | 10.9 | 10.2 | 3.4 |
| Tensile Strength/MPa | 31 | 30 | 31 | 35 | 34 | 8 |
| Tensile shear Strength/MPa of Steel | 20 | 28 | 24 | 24 | 26 | 5 |
| Impact height/cm | 80 | 72 | 74 | 83 | 81 | 25 |
When the product prepared by the invention in the table 1 is used as a flexible LED packaging material, the tensile property, bending resistance and impact resistance of a cured product can be effectively enhanced, the toughening effect is achieved, the product has excellent elastic recovery and stress absorption capacity, and the service life of the flexible LED under the use scene can be obviously prolonged.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.
Claims (6)
1. A phenyl silicone resin containing a branched structure, characterized in that the resin has a structure represented by formula 1:
wherein n is an integer of 1 or more, preferably n is 10 to 40, m is an integer of 1 or more, preferably m is 3 to 6.
2. A process for preparing a phenyl silicone resin containing a branched structure, said resin being the resin according to claim 1, characterized in that it comprises the steps of:
s1: the mixed ring of methyl phenyl siloxane and 1, 3-tetramethyl disiloxane are subjected to ring-opening polymerization reaction under the action of an acid catalyst, the acid catalyst is neutralized after the reaction, and unreacted small molecules are removed after filtering solids, so that a compound shown in a formula 3 is obtained:
wherein n is an integer not less than 1, preferably n is 10 to 40;
s2: carrying out addition reaction on a compound of formula 3 and enamine under the action of a rhodium catalyst, and removing unreacted small molecules to obtain a compound of formula 2:
wherein n is an integer not less than 1, preferably n is 10 to 40, m is an integer not less than 1, preferably m is 3 to 6;
s3: and (3) carrying out condensation reaction on the compound shown in the formula 2 and vinyl phosphonic acid, and removing unreacted micromolecules to obtain a target product shown in the formula 1.
3. The method of claim 2, wherein the methyl phenyl siloxane hybrid ring of S1 comprises one or more of 2,4, 6-trimethyl-2, 4, 6-triphenyl cyclotrisiloxane, 2,4,6, 8-tetramethyl-2, 4,6, 8-tetraphenyl cyclotetrasiloxane, and 2,4,6,8, 10-pentamethyl-2, 4,6,8, 10-pentamphenyl cyclopentasiloxane;
preferably, the mass ratio of the methyl phenyl siloxane mixed ring body to the 1, 3-tetramethyl disiloxane is (12.6-50.7): 1;
and/or, the reaction of S1 is carried out under inert atmosphere;
and/or the acid catalyst of S1 is fluorine-containing organic acid with 1-7 carbon atoms, preferably trifluoro methane sulfonic acid;
preferably, the dosage of the acid catalyst is 1 to 5 per mill of the total mass of the mixed ring body of the methyl phenyl siloxane and the 1, 3-tetramethyl disiloxane;
and/or the reaction temperature of S1 is 60-80 ℃ and the reaction time is 3-4 h;
and/or, the neutralization of S1 adopts carbonate, preferably carbonate is one or more of alkali metal carbonate, more preferably calcium carbonate;
preferably, the carbonate is used in an amount of 3-5% of the total mass of the mixed ring body of the methyl phenyl siloxane and the 1, 3-tetramethyl disiloxane;
preferably, the reaction time of the carbonate neutralization acid catalyst is 1-2 h;
and/or, the devolatilizing and removing unreacted small molecules in the S1 step adopts a short-path evaporator;
preferably, the temperature for removing unreacted small molecules is 100-120 ℃ and the pressure is 0.1 KPaA-1 KPaA.
4. The method according to claim 2, characterized in that S2 said enamine is a C3-C6 enamine, preferably one or more of an propenamine, 3-butene-1-amine, 4-pentene-1-amine, 5-hexene-1-amine, more preferably 3-butene-1-amine;
preferably, the molar ratio of the compound of formula 3 to enamine is 1 (2-2.4);
and/or, the reaction of S2 is carried out under inert atmosphere;
and/or the rhodium catalyst in S2 is one or more of tris (triphenylphosphine) rhodium (I) chloride, triphenylphosphine acetylacetonato rhodium (I) carbonyl and rhodium (I) 2-ethylhexanoate;
preferably, the rhodium catalyst is used in an amount of 1 to 5ppm based on the total mass of the compound of formula 3 and enamine calculated as rhodium;
and/or the reaction temperature of S2 is 40-60 ℃ and the reaction time is 2-4 h;
and/or the temperature for removing unreacted micromolecules is 60-80 ℃ and the pressure is 0.1 KPaA-1 KPaA.
5. The process according to claim 2, wherein the molar ratio of the compound of formula 2 to vinylphosphonic acid of S3 (2 to 2.5) is 1;
and/or S3, wherein the reaction temperature is 80-100 ℃ and the reaction time is 8-10 h;
and/or the temperature for removing unreacted micromolecules is 100-120 ℃ and the pressure is 0.1 KPaA-1 KPaA.
6. Use of a phenyl silicone resin containing a branched structure, said resin being a resin according to claim 1, or a resin prepared by a method according to any one of claims 2 to 5, characterized in that said resin is used for encapsulation of high refractive index flexible LEDs.
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