CN112830934B - Unsaturated spiro orthocarbonate expansion monomer and synthesis method and application thereof - Google Patents
Unsaturated spiro orthocarbonate expansion monomer and synthesis method and application thereof Download PDFInfo
- Publication number
- CN112830934B CN112830934B CN202110216695.7A CN202110216695A CN112830934B CN 112830934 B CN112830934 B CN 112830934B CN 202110216695 A CN202110216695 A CN 202110216695A CN 112830934 B CN112830934 B CN 112830934B
- Authority
- CN
- China
- Prior art keywords
- reaction
- reaction liquid
- orthocarbonate
- monomer
- toluene
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/10—Spiro-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on 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; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
-
- 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
Abstract
The invention provides an unsaturated spiro orthocarbonate expansion monomer, and a synthesis method thereof comprises the following steps: (1) weighing 6, 8-dihydroxy-1-nonene, di-n-butyltin oxide and toluene, adding into a reaction vessel, stirring, and reacting at 150 +/-2 ℃; (2) cooling the reaction liquid in the reaction container to room temperature, then dropwise adding carbon disulfide into the reaction liquid, heating the reaction liquid to 110 +/-2 ℃, and continuing to react; (3) and cooling the reaction liquid to room temperature, removing toluene in the reaction liquid, washing, recrystallizing and drying in vacuum to obtain the unsaturated spiro orthocarbonate expansion monomer. The unsaturated spiro orthocarbonate expansion monomer can be used as a curing shrinkage prevention component of an organic silicon resin packaging material. The unsaturated spiro orthocarbonate expansion monomer synthesized by the invention can not only expand through ring-opening polymerization, but also react with vinyl monomers, acrylic resin or vinyl hydrogen-containing silicone resin, so that the resin shrinkage rate can be reduced.
Description
Technical Field
The invention relates to an expansion monomer, in particular to a synthetic method of an unsaturated spiro orthocarbonate expansion monomer and application of the unsaturated spiro orthocarbonate expansion monomer in preparation of an organic silicon resin packaging material.
Background
The thermosetting resin inevitably generates volume shrinkage in the curing process, so that shrinkage stress is generated and becomes a potential damage factor, which causes the strength of the material to be sharply reduced and even causes the material to crack; or cause the performance deterioration and parameter drift of electronic or optical components; or the cementing interface is more easily affected by environmental factors such as water, acid and the like. The reasons for curing shrinkage include solvent molecule overflow, small molecule elimination, and the change of van der Waals' force between monomer molecules into covalent bond after curing. The traditional method for reducing curing shrinkage comprises the steps of reducing the concentration of functional groups in a reaction system by adopting copolymerization or prepolymerization, adding an inorganic filler, adding a macromolecular toughening agent, improving process conditions and the like. However, in any of the methods, the volume shrinkage can be reduced, and the volume shrinkage cannot be completely eliminated. Research shows that the polymerization reaction of the spiro compound has the advantages that the spiro compound has more links along with the increase of monomer rings, the volume shrinkage is continuously reduced, and even the volume does not change or generate volume expansion, so the resin curing shrinkage can be counteracted by adopting the copolymerization reaction of the expansion monomers.
When the expansion monomer is applied to an epoxy resin cation curing system, the spiro group and the epoxy group can carry out ring-opening copolymerization reaction, and the conversion rate of the epoxy group can be improved by adding the expansion monomer. This is because, in the initial stage of the reaction, the ring-opening reaction between epoxy groups is mainly performed; with the reaction, the mobility of the epoxy group is limited after a cross-linking structure is preliminarily formed, and the active cation lengthening chain is difficult to collide with the unreacted epoxy group but can still collide with a plurality of spiro groups with great mobility in the system; when the cation attacks the oxygen of the expansion monomer to form oxygen positive ions, the oxygen positive ions are quickly isomerized, the first ring in the spiral ring of the expansion monomer is opened to form carbocation, the carbocation continuously attacks other expansion monomers, the second ring in the spiral ring of the expansion monomer is also opened, so that double ring-opening copolymerization reaction is carried out, and a branched chain or a cross-linked structure is generated; the incompletely reacted spiro group can be further self-polymerized to form an interpenetrating network structure. This structure increases the flexibility of the polymer network, thereby reducing the internal stress of the epoxy resin.
However, since the general spiro orthocarbonate expansion monomer does not contain other active functional groups and cannot react with alkene monomers, organic silicon resins and the like, the shrinkage reduction effect of the general spiro orthocarbonate expansion monomer in other thermosetting resin systems is obviously inferior to that of epoxy resins, which limits further wide application of the expansion monomer.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a synthesis method and application of an unsaturated spiro orthocarbonate expansion monomer, wherein the synthesized unsaturated spiro orthocarbonate expansion monomer can expand through ring-opening polymerization, can react with an olefin monomer, acrylic resin or vinyl hydrogen-containing silicone resin, can better adapt to more complex and various resin systems, can better play the expansion effect of the expansion monomer, and can reduce the resin shrinkage rate. The technical scheme is as follows:
an unsaturated spiro orthocarbonate swelling monomer is characterized in that the structural formula is as follows:
the synthesis method of the unsaturated spiro orthocarbonate expansion monomer is characterized by comprising the following steps:
(1) weighing 6, 8-dihydroxy-1-nonene, di-n-butyltin oxide and toluene, adding into a reaction container, stirring, and reacting at 150 +/-2 ℃ for 12-14 hours or until no water is generated;
the molar ratio of the 6, 8-dihydroxy-1-nonene to the di-n-butyltin oxide is 1: 1;
the step is carried out according to a reaction formula (I), and generated water is continuously removed in the reaction process;
(2) cooling the reaction liquid in the reaction container to room temperature (20-30 ℃), then dropwise adding carbon disulfide into the reaction liquid, heating the reaction liquid to 110 +/-2 ℃, and continuing to react for 12-14 hours;
the step is carried out according to a reaction formula (II) and a reaction formula (III);
(3) and cooling the reaction liquid to room temperature, removing toluene in the reaction liquid, washing the reaction liquid by using n-hexane, recrystallizing, and drying a recrystallized product in vacuum to obtain the unsaturated spiro orthocarbonate expansion monomer.
In a specific scheme, in the step (1), a three-neck flask placed in an oil bath pot is adopted as a reaction container, 6, 8-dihydroxy-1-nonene, di-n-butyl tin oxide and toluene are added into the three-neck flask, a water separator and a reflux condenser pipe are installed, a calcium chloride drying pipe is installed on the reflux condenser pipe, and then reaction is carried out; in the step (2), after the reaction liquid is cooled to room temperature, removing the water separator, installing a constant-pressure dropping funnel, adding carbon disulfide into the funnel, slowly dropping the carbon disulfide into the reaction liquid, gradually heating the reaction liquid to 110 +/-2 ℃, and continuously carrying out reflux reaction for 12-14 hours; in the step (3), the reaction solution is cooled to room temperature, toluene in the reaction solution is distilled out under reduced pressure by using a vacuum pump, then n-hexane is used for washing for a plurality of times (the n-hexane can be added into a reaction container for washing, oily viscous liquid at the bottom of the reaction container is a relatively pure monomer, preferably, the washing time is 5-10 times), then recrystallization is carried out in toluene, and the unsaturated spiro orthocarbonate expansion monomer is obtained after the toluene is removed by vacuum drying (the obtained unsaturated spiro orthocarbonate expansion monomer is a white solid).
The reaction temperature in the step (1) is controlled to be 150 +/-2 ℃, so that the generation of unexpected side reactions can be reduced, and the product yield is improved; the reaction time is 12-14 hours (or the reaction is carried out till no water is generated), the reaction can be fully carried out, and the product yield is improved; the water generated in the reaction process is continuously removed, which is favorable for promoting the reaction to be carried out in the forward direction.
In the step (2), "slowly dropping" is to ensure that the dropwise added carbon disulfide can be rapidly and uniformly dispersed after entering the reaction solution, so as to avoid causing too high local concentration, and only ensure uniform dispersion. Typically, the reaction solution is also stirred during the dropwise addition of carbon disulfide to promote rapid and uniform dispersion of carbon disulfide.
In the step (2), the whole reaction solution should be uniformly heated during the heating process, so as to avoid over-high local temperature.
Preferably, in the step (2), the molar ratio of the carbon disulfide to the reaction product in the step (1) is (0.5-1): 1. Theoretically, the molar ratio of the carbon disulfide to the reaction product in the step (1) is 1:2, but in practice, the addition amount of the carbon disulfide is more than the theoretical amount due to the concentration of reactants, steric hindrance of the reaction and the like, so that the reaction of the reaction formula (II) and the reaction formula (III) can be fully carried out.
In the step (3), the toluene is distilled off, and the product of the unsaturated spiro orthocarbonate expanded monomer is obtained after n-hexane washing, but the product may still wrap other unreacted raw materials, byproducts, impurities and the like, so recrystallization is required for further purification. The specific steps of recrystallization generally include: and (3) reheating and dissolving the product in toluene, filtering to remove insoluble impurities, cooling the filtrate, separating out the product in the form of crystals, performing suction filtration to remove toluene, and drying the crystals to obtain the unsaturated spiro orthocarbonate expanded monomer with high purity.
The application of the unsaturated spiro orthocarbonate expansion monomer in preparing the organic silicon resin packaging material is characterized in that the unsaturated spiro orthocarbonate expansion monomer is used as a curing shrinkage prevention component of the organic silicon resin packaging material.
In a preferred embodiment, the silicone resin sealing material comprises, by weight: 65-75 parts of vinyl silicone resin, 18-22 parts of hydrogen-containing silicone oil, 8-12 parts of hydrogen-containing silicone resin, 0.02-0.08 part of catalyst, 0.8-1.5 parts of inhibitor, 5-12 parts of coupling agent and 10-40 parts of unsaturated spiro orthocarbonate expansion monomer.
More preferably, the vinyl silicon resin has a vinyl group content of 2%, the hydrogen content of the hydrogen-containing silicone oil is 4.5%, the hydrogen content of the hydrogen-containing silicone resin is 9%, the catalyst is a platinum catalyst with a platinum content of 3000ppm, the inhibitor is an alkynol inhibitor, and the coupling agent is a coupling agent KH 550.
The invention has the beneficial effects that:
(1) an unsaturated spiro orthocarbonate expansion monomer is synthesized, the unsaturated spiro orthocarbonate expansion monomer can expand through ring-opening polymerization, and meanwhile, due to the existence of unsaturated double bonds, the unsaturated spiro orthocarbonate expansion monomer can react with an alkene monomer, acrylic resin or vinyl hydrogen-containing silicone resin, so that the unsaturated spiro orthocarbonate expansion monomer can better adapt to more complicated and various resin systems, better exert the expansion effect of the expansion monomer and reduce the shrinkage rate of the resin;
(2) when the unsaturated spiro orthocarbonate expansion monomer is applied to the curing shrinkage prevention component of the organic silicon resin packaging material, the unsaturated spiro orthocarbonate expansion monomer is copolymerized with resin to form an interpenetrating network structure, so that the internal stress of the resin is reduced, and the toughness of the resin is obviously enhanced;
(3) due to the action of the unsaturated spiro orthocarbonate expansion monomer, the volume of matrix resin is not shrunk in the curing process, the interface bonding condition between the resin and the carrier is good, and the bonding force of the resin is improved.
Detailed Description
Example 1
In this embodiment, the method for synthesizing the unsaturated spiro orthocarbonate monomer includes the following steps:
(1) weighing 6, 8-dihydroxy-1-nonene, di-n-butyltin oxide and toluene (0.1 mol of 6, 8-dihydroxy-1-nonene, 0.1mol of di-n-butyltin oxide and 150ml of toluene), adding the materials into a reaction container, stirring, reacting at 150 +/-2 ℃ for 12 hours or until no water is generated (in the step (1), adding the 6, 8-dihydroxy-1-nonene, the di-n-butyltin oxide and the toluene into a three-neck flask by adopting the three-neck flask placed in an oil bath kettle, then installing a water separator and a reflux condenser pipe, installing a calcium chloride drying pipe on the reflux condenser pipe, and then reacting);
the step is carried out according to a reaction formula (I), and generated water is continuously removed in the reaction process;
(2) cooling the reaction liquid in the reaction container to room temperature, dropwise adding carbon disulfide (the dropwise adding amount of the carbon disulfide is 0.08 mol) into the reaction liquid, heating the reaction liquid to 110 +/-2 ℃, and continuing to react for 12 hours (in the step (2), after cooling the reaction liquid to the room temperature, removing a water separator, installing a constant-pressure dropping funnel, adding the carbon disulfide into the funnel, slowly dropwise adding the carbon disulfide into the reaction liquid, gradually heating the reaction liquid to 110 +/-2 ℃, and continuing to reflux and react for 12 hours);
the step is carried out according to a reaction formula (II) and a reaction formula (III);
(3) and cooling the reaction liquid to room temperature, removing toluene in the reaction liquid, washing the reaction liquid by using n-hexane, recrystallizing, and drying a recrystallized product in vacuum to obtain the unsaturated spiro orthocarbonate expansion monomer.
In the step (3), the reaction solution is cooled to room temperature, toluene in the reaction solution is distilled out under reduced pressure by using a vacuum pump, then n-hexane is used for washing for a plurality of times (the n-hexane is added into a reaction container for washing, oily viscous liquid at the bottom of the reaction container is a relatively pure monomer, the washing times are 5 times), then recrystallization is carried out in toluene (the dosage of the toluene is 50 ml), and the unsaturated spiro orthocarbonate expansion monomer is obtained after the toluene is removed by vacuum drying (the obtained unsaturated spiro orthocarbonate expansion monomer is white solid).
The structural formula of the prepared unsaturated spiro orthocarbonate expansion monomer is as follows:
the unsaturated spiro orthocarbonate expansion monomer is used as a curing shrinkage prevention component of the organic silicon resin packaging material.
In this example, the silicone resin encapsulating material contains by weight: 70 parts of vinyl silicone resin (the vinyl content of the vinyl silicone resin is 2%), 20 parts of hydrogen-containing silicone oil (the hydrogen content of the hydrogen-containing silicone oil is 4.5%), 10 parts of hydrogen-containing silicone resin (the hydrogen content of the hydrogen-containing silicone resin is 9%), 0.05 part of catalyst (the catalyst is platinum catalyst with the platinum content of 3000 ppm), 1 part of inhibitor (the inhibitor is alkynol inhibitor), 8 parts of coupling agent (the coupling agent is KH 550), and 20 parts of unsaturated spirocyclic orthocarbonate swelling monomer. Weighing the raw materials according to the proportion, and uniformly mixing to obtain the organic silicon resin packaging material.
Comparative example 1
Weighing the following raw materials in parts by weight: 70 parts of vinyl silicone resin with 2 percent of vinyl content, 20 parts of hydrogen-containing silicone oil with 4.5 percent of hydrogen content, 10 parts of hydrogen-containing silicone resin with 9 percent of hydrogen content, 0.05 part of platinum catalyst with 3000ppm of platinum content, 1 part of alkynol inhibitor and 8 parts of KH550 coupling agent. The raw materials are weighed according to the proportion and are uniformly mixed to prepare the organic silicon resin packaging material (without the expansion monomer).
Comparative example 2
Weighing the following raw materials in parts by weight: 70 parts of vinyl silicone resin with 2 percent of vinyl content, 20 parts of hydrogen-containing silicone oil with 4.5 percent of hydrogen content, 10 parts of hydrogen-containing silicone resin with 9 percent of hydrogen content, 0.05 part of platinum catalyst with 3000ppm of platinum content, 1 part of alkynol inhibitor, 8 parts of KH550 coupling agent and 20 parts of common swelling monomer. Weighing the raw materials according to the proportion, and uniformly mixing to obtain the organic silicon resin packaging material.
The common expansion monomer is 1,5,7, 11-tetraoxaspiro [5,5] undecane, and the structural formula is as follows:
test samples were taken from the silicone resin encapsulating materials prepared in example 1, comparative example 1 and comparative example 2, and heat-cured to obtain a mass, which was tested for volume shrinkage, flexural strength and shear strength, and the results are shown in table 1.
TABLE 1
| Comparative example 1 | Comparative example 2 | Example 1 | |
| Volume shrinkage rate | 8.2% | 6.4% | 1.3% |
| Bending strength | 62 MPa | 68 MPa | 94 MPa |
| Shear strength | 2.3 MPa | 2.4 MPa | 4.1 MPa |
As can be seen from table 1 above, compared with the common expansion monomer, the unsaturated spiro orthocarbonate expansion monomer of the present invention can more effectively reduce the volume shrinkage of the silicone resin encapsulating material system, improve the toughness strength of the matrix resin, and enhance the adhesive capacity of the resin.
Claims (7)
1. An unsaturated spiro orthocarbonate swelling monomer is characterized in that the structural formula is as follows:
2. the method for synthesizing an unsaturated spirocyclic orthocarbonate swelling monomer according to claim 1, comprising the steps of:
(1) weighing 6, 8-dihydroxy-1-nonene, di-n-butyltin oxide and toluene, adding into a reaction container, stirring, and reacting at 150 +/-2 ℃ for 12-14 hours or until no water is generated;
the molar ratio of the 6, 8-dihydroxy-1-nonene to the di-n-butyltin oxide is 1: 1;
the step is carried out according to a reaction formula (I), and generated water is continuously removed in the reaction process;
(2) cooling the reaction liquid in the reaction container to room temperature, then dropwise adding carbon disulfide into the reaction liquid, heating the reaction liquid to 110 +/-2 ℃, and continuing to react for 12-14 hours;
the step is carried out according to a reaction formula (II) and a reaction formula (III);
(3) and cooling the reaction liquid to room temperature, removing toluene in the reaction liquid, washing the reaction liquid by using n-hexane, recrystallizing, and drying a recrystallized product in vacuum to obtain the unsaturated spiro orthocarbonate expansion monomer.
3. The method for synthesizing an unsaturated spirocyclic orthocarbonate monomer according to claim 2, wherein: in the step (1), a reaction container adopts a three-neck flask which is placed in an oil bath kettle, 6, 8-dihydroxy-1-nonene, di-n-butyl tin oxide and toluene are added into the three-neck flask, a water separator and a reflux condenser pipe are installed, a calcium chloride drying pipe is installed on the reflux condenser pipe, and then reaction is carried out; in the step (2), after the reaction liquid is cooled to room temperature, removing the water separator, installing a constant-pressure dropping funnel, adding carbon disulfide into the funnel, slowly dropping the carbon disulfide into the reaction liquid, gradually heating the reaction liquid to 110 +/-2 ℃, and continuously carrying out reflux reaction for 12-14 hours; and (3) cooling the reaction liquid to room temperature, distilling out toluene in the reaction liquid under reduced pressure by using a vacuum pump, washing the toluene for 5-10 times by using n-hexane, recrystallizing the toluene, and drying the toluene in vacuum to remove the toluene to obtain the unsaturated spiro orthocarbonate expansion monomer.
4. The method for synthesizing an unsaturated spirocyclic orthocarbonate monomer according to claim 2, wherein: in the step (2), the molar ratio of the carbon disulfide to the reaction product in the step (1) is (0.5-1): 1.
5. The use of the unsaturated spirocyclic orthocarbonate swelling monomer according to claim 1 in the preparation of a silicone resin encapsulant, wherein said unsaturated spirocyclic orthocarbonate swelling monomer is used as a cure shrinkage prevention component of a silicone resin encapsulant.
6. Use of an unsaturated spirocyclic orthocarbonate swelling monomer according to claim 5 in the preparation of a silicone resin encapsulant, characterized in that said silicone resin encapsulant comprises by weight: 65-75 parts of vinyl silicone resin, 18-22 parts of hydrogen-containing silicone oil, 8-12 parts of hydrogen-containing silicone resin, 0.02-0.08 part of catalyst, 0.8-1.5 parts of inhibitor, 5-12 parts of coupling agent and 10-40 parts of unsaturated spiro orthocarbonate expansion monomer.
7. The use of the unsaturated spirocyclic orthocarbonate swelling monomer according to claim 6 in the preparation of silicone resin encapsulating materials, characterized in that: the vinyl content of the vinyl silicon resin is 2%, the hydrogen content of the hydrogen-containing silicone oil is 4.5%, the hydrogen content of the hydrogen-containing silicone resin is 9%, the catalyst is a platinum catalyst with the platinum content of 3000ppm, the inhibitor is an alkynol inhibitor, and the coupling agent is a coupling agent KH 550.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110216695.7A CN112830934B (en) | 2021-02-26 | 2021-02-26 | Unsaturated spiro orthocarbonate expansion monomer and synthesis method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110216695.7A CN112830934B (en) | 2021-02-26 | 2021-02-26 | Unsaturated spiro orthocarbonate expansion monomer and synthesis method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112830934A CN112830934A (en) | 2021-05-25 |
| CN112830934B true CN112830934B (en) | 2022-04-12 |
Family
ID=75933803
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110216695.7A Active CN112830934B (en) | 2021-02-26 | 2021-02-26 | Unsaturated spiro orthocarbonate expansion monomer and synthesis method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112830934B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114989187A (en) * | 2021-11-03 | 2022-09-02 | 深圳市撒比斯科技有限公司 | Spiro-carbon ortho ester and preparation method thereof |
| CN115433204B (en) * | 2022-09-27 | 2024-01-19 | 深圳市安伯斯科技有限公司 | Synthesis method and application of spiro-expandable monomer with multi-benzene ring structure |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5463008A (en) * | 1992-03-06 | 1995-10-31 | The United States Of America As Represented By The Secretary Of Commerce | Monomers for double ring-opening polymerization with expansion |
| CN101712800A (en) * | 2009-11-06 | 2010-05-26 | 陈俊光 | Organic silicon resin encapsulant of large power LED and preparing method thereof |
| CN102199158A (en) * | 2011-04-15 | 2011-09-28 | 沈阳化工大学 | Synthesis method for 2-decyl-2-dihydroxymethyl propylene spiro-orthocarbonate monomer |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100943421B1 (en) * | 2007-12-24 | 2010-02-19 | 연세대학교 산학협력단 | Photopolymerizable monomers having epoxide and undaturated double bonds and their composition |
| CN103626786B (en) * | 2013-11-20 | 2015-09-30 | 沈阳化工大学 | A kind of synthetic method of chloride screw ring orthocarbonicester monomer |
-
2021
- 2021-02-26 CN CN202110216695.7A patent/CN112830934B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5463008A (en) * | 1992-03-06 | 1995-10-31 | The United States Of America As Represented By The Secretary Of Commerce | Monomers for double ring-opening polymerization with expansion |
| CN101712800A (en) * | 2009-11-06 | 2010-05-26 | 陈俊光 | Organic silicon resin encapsulant of large power LED and preparing method thereof |
| CN102199158A (en) * | 2011-04-15 | 2011-09-28 | 沈阳化工大学 | Synthesis method for 2-decyl-2-dihydroxymethyl propylene spiro-orthocarbonate monomer |
Non-Patent Citations (2)
| Title |
|---|
| Spiro Orthocarbonate Undertaking Radical and Cationic Polymerization;Takeshi Endo et al.;《Macromolecules》;19871231;第20卷(第11期);第2690-2693页 * |
| 不饱和螺环原碳酸酯膨胀单体的合成;刘小青等;《口腔新材料的临床应用技术研讨会论文集》;20050630;第35-36页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112830934A (en) | 2021-05-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112830934B (en) | Unsaturated spiro orthocarbonate expansion monomer and synthesis method and application thereof | |
| CN1150810A (en) | Moisture-curable modified acrylic polymer sealant composition | |
| CN107880263B (en) | Temperature-responsive clustering peptide with side chain containing oligo-polyethylene glycol and preparation method thereof | |
| CN108192563B (en) | Synthesis method of high-temperature-resistant tackifier | |
| WO2017146444A1 (en) | Method for preparing (meth)acrylate group-containing benzophenone for optical adhesive, and optical adhesive composition | |
| CN100344674C (en) | Adhesive compositions containing hybrid oxetane compounds | |
| CN101058585A (en) | Safe separation method for increasing yield of methyl phenyl dialkoxy silicane | |
| CN112691705B (en) | Preparation method of acid-binding functional catalyst for synthesizing methyl tributyl ketoxime silane | |
| EP2739656B1 (en) | An oxazolidone ring containing vinyl ester resin and products therefrom | |
| CN110128464B (en) | Preparation method of methyldimethoxysilane | |
| TWI520987B (en) | Cage silsesquioxane silicone resin and siloxane cage silsesquioxane silicone siloxane copolymer, and manufacturing method thereof | |
| TW321634B (en) | ||
| CN111484620B (en) | Adhesion promoter for addition type silicone rubber, preparation method and application thereof | |
| CN110835391A (en) | Unsaturated polyester resin curing accelerator and preparation method and application thereof | |
| CN107778325B (en) | Preparation method of N- [3- (trimethoxysilyl) propyl ] N-butylamine | |
| CN112625219A (en) | Synthesis method of trapezoidal oligomer | |
| KR102553747B1 (en) | UV-curable dismantling Pressure sensitive adhesive(PSA) composition and Manufacturing method thereof | |
| CN1448417A (en) | Prep. of high softening point and high fusion viscosity pentadiene petroleum resin | |
| CN111171205B (en) | Production method of polypropylene | |
| CN116178723A (en) | Epoxy modified organic silicon resin and yellowing-resistant chip adhesive | |
| CN114015037A (en) | Synthesis method and application of silane terminated polyether | |
| CN117069758A (en) | Hyperbranched rosin-based organosilane crosslinking agent, preparation method and application thereof | |
| WO2023095556A1 (en) | Production method for (meth)acryloyl group-containing organopolysiloxane | |
| CN114805740A (en) | Solvent-free TDI tripolymer urethane acrylate and preparation method thereof | |
| CN1730498A (en) | A vanadium catalyst and its preparation method |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |