CN106589786A - L-POSS crosslinking agent contained isomerism modified polyformaldehyde and preparation method thereof - Google Patents
L-POSS crosslinking agent contained isomerism modified polyformaldehyde and preparation method thereof Download PDFInfo
- Publication number
- CN106589786A CN106589786A CN201611223474.8A CN201611223474A CN106589786A CN 106589786 A CN106589786 A CN 106589786A CN 201611223474 A CN201611223474 A CN 201611223474A CN 106589786 A CN106589786 A CN 106589786A
- Authority
- CN
- China
- Prior art keywords
- poss
- isomerism
- pom
- linking agent
- cross
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2359/00—Characterised by the use of polyacetals containing polyoxymethylene sequences only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/16—Ethene-propene or ethene-propene-diene copolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2459/00—Characterised by the use of polyacetals containing polyoxymethylene sequences only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Abstract
The invention discloses L-POSS crosslinking agent contained isomerism modified polyformaldehyde and a preparation method thereof, and relates to polyformaldehyde and a preparation method thereof. The method comprises the steps that recycled POM is dried; a home-made micro-crosslinking master batch is smashed and ground, then, the dried recycled hard POM, the micro-crosslinking master batch, a thermal stabilizer and inorganic filler are put into a high mixing machine according to the weight ratio to be mixed, and finally a two-screw extruder is used for extrusion pelletizing to obtain reclaimed materials. The effects of enhancing, toughening and recycling POM can be achieved at the same time. In addition, the L-POSS crosslinking agent adopts Si-O as an inorganic core, the good heat resistance and flame resistance and the excellent water resistance, radiation resistance and electric performance are achieved due to the inorganic core, and a certain promotion effect in the machining process can be achieved. Due to introduction of the isomerism crosslinking method, the tenacity and strength of regenerated POM can be good without adding a compatilizer in the POM recycling regeneration process, and the quite good market promotion value is achieved.
Description
Technical field
The present invention relates to a kind of polyformaldehyde and preparation method thereof, more particularly to a kind of isomerism of cross-linking agent containing L-POSS
Modified polyacetal and preparation method thereof.
Background technology
L-POSS cross-linking agent is the synthetic method using L-POSS with silane compound reaction, synthesizes novel silane crosslinking
Agent.Product is the derivant of silane, is catalyzed the active site that silane is produced under initiation and forms polyaddition reaction with-LPOSS,
The cross-linking agent with double crosslinked actions is formed, at the same time, because L-POSS is different from traditional Organic substance, it is as nothing with Si-O
Machine kernel, inorganic kernel can give its good thermostability, flame resistance, splendid resistance to water, radioactivity and electrical property, so
The novel silane cross-linking agent containing L-POSS of synthesis also has greatly improved in these performances, therefore this silane crosslinker can be
High temperature, the lower presence of high radiation, and its cross-linking agent performance of doing more independent than silane is more preferable, and the cost of cross-linking agent is also directly done than POSS
Much smaller, cross-linking effect is more preferable, performance also gets a promotion.
Polyformaldehyde (English：Polyformaldehyde) also known as acetal resin, its have good physics, mechanically and chemically property
Can, especially there is excellent crocking resistance, be the third-largest general-purpose plastics.Be suitable to make anti-attrition wear part, driving parts,
And chemical industry, the part such as instrument.Property it is good, fatigue durability project, be difficult by chemical mediator corrode etc..In recent years, as industry is sent out
The demand of exhibition, concern of the people to the study on the modification of polyformaldehyde also all the more.Polyformaldehyde (POM) is with less than other many engineering plastics
Cost, substituting some markets traditionally captured by metal, such as substituting zinc, pyrite, aluminum and steel and make many parts,
Since the advent of the world, POM have been widely used for the field such as electric, mechanical, instrument, daily light industry, automobile, building materials, agricultural.
In the application of many frontiers, such as in terms of medical skill, sports apparatus etc., POM also shows preferable growing trend.
On the other hand, POM is corroded by strong acid, and weather resisteant is poor, poor adhesion, and thermal decomposition is close to softening temperature, and limit oxygen refers to
The shortcomings of counting little, shock resistance is poor limits its application, it is therefore desirable to which which is modified, and this patent passes through L-POSS cross-linking agent
The preparation method of the modified POM of isomerism cross-linking method activeness and quietness carried out to which be modified.
The content of the invention
It is an object of the invention to provide a kind of isomerism modified polyacetal of cross-linking agent containing L-POSS and preparation method thereof,
The present invention containing L-POSS structures cross-linking agent be with Si-O as inorganic kernel, inorganic kernel can give its good thermostability,
Flame resistance, splendid resistance to water, radioactivity and electrical property, can play certain facilitation in process, can be simultaneously real
The effect of POM is reclaimed in now enhancing, toughness reinforcing.
The purpose of the present invention is achieved through the following technical solutions：
A kind of isomerism modified polyacetal of cross-linking agent containing L-POSS, described L-POSS cross-linking agent is using L-POSS and silicon
The method of hydride compounds reaction, product is the derivant of silane；Its structure is：
；
Based on mass weight part, its component is isomerism modified polyacetal：
Reclaim 100 parts of polyformaldehyde；
10～30 parts of toughener；
10～30 parts of crosslinking masterbatch；
10～20 parts of inorganic filler；
3～20 parts of heat stabilizer.
Described one kind cross-linking agent containing L-POSS isomerism modified polyacetal, the synthetic cross-linking agent include two ranks
Section, is to form raw material first, next to that silane produces active site so as to introduce L-POSS formation chemical reactions under catalytic action
Prepare silane crosslinker containing L-POSS.
Described one kind cross-linking agent containing L-POSS isomerism modified polyacetal, the toughener are POM/POE, POM/
At least one in EVA.
Described one kind cross-linking agent containing L-POSS isomerism modified polyacetal, the crosslinking masterbatch are by A material B material and produce water
Three step part of agent constitutes；
A expects composition:Polyformaldehyde
The cross-linking agent of structure novel containing L-POSS
Initiator（Cumyl peroxide (DCP)）
B expects composition：Polyformaldehyde
Catalyst（Dibutyl tin laurate）
Antioxidant（Antioxidant 1010）
Produce water preparation composition：Acid and metal-oxide；The acid produced in water preparation is stearic acid, at least one in mineral acid；Metal oxygen
Compound is Zinc Oxide, at least one in stannum oxide.
Described one kind cross-linking agent containing L-POSS isomerism modified polyacetal, described filler is Calcium Carbonate, in Pulvis Talci
At least one.
Described one kind cross-linking agent containing L-POSS isomerism modified polyacetal, the heat stabilizer are phosphorous triphenyl phosphate
Ester.
A kind of isomerism modified polyacetal preparation method of cross-linking agent containing L-POSS, the method comprising the steps of：
A, 95 parts of A material is weighed by mass fraction, after 4.5 parts of B material mixing, is put into extruding pelletization in double screw extruder, then again with
0.5 part of product water preparation（Stearic acid and Zinc Oxide 1:1 mixture）Mix homogeneously is put into double screw extruder extruding pelletization and forms friendship
Connection masterbatch；
B, the micro- crosslinking masterbatch in A portions are first put into Universalpulverizer grinding are placed in planetary ball mill until crosslinking masterbatch
Particle diameter reach 10～50 μm till；
C, hard POM materials forced air drying 6～8 hours under the conditions of 80 DEG C will be reclaimed, by weight ratio by micro- crosslinking masterbatch, heat
Stabilizer, recovery hard POM, inorganic filler mix 4～6 minutes in putting into high-speed mixer so as to uniform to mix；
D, the material of the above-mentioned mix homogeneously in high-speed mixer is added to screw slenderness ratio for 36, rotating speed is 200r/min's
In double screw extruder, the mean diameter of micro- crosslinking masterbatch is controlled 10 using the Strong shear power of twin screw in the molten state
～50 μm, while crosslinking material is mixed homogeneously with heat stabilizer, reclaimed materials and inorganic filler, by above-mentioned compound extruding pelletization
Obtain the regeneration hard POM containing crosslinking POM.
Described one kind cross-linking agent containing L-POSS isomerism modified polyacetal preparation method, the double screw extruder
Extruder temperature control is between 160 DEG C -180 DEG C.
Advantages of the present invention with effect is：
The present invention can realize that the effect of POM is reclaimed in enhancing, toughness reinforcing simultaneously.On the other hand, the cross-linking agent containing L-POSS structures be with
Si-O is inorganic kernel, and inorganic kernel can give its good thermostability, flame resistance, splendid resistance to water, radioactivity and electricity
Performance, can play certain facilitation in process.And the introducing of isomerism cross-linking method can make recovery POM's
Need not add compatilizer that the toughness and intensity of regeneration POM can also be made fine in regenerative process, great market popularization value.
Description of the drawings
Fig. 1 is the reaction equation of L-POSS and the synthesis high temperature resistant cross-linking agent of vinyltrimethoxy silane.
Specific embodiment
With reference to embodiment, the present invention is described in detail.
Embodiment 1-3, in each embodiment, the weight distribution ratio of each component is as shown in table 1.Each component is weighed by proportioning,
Mix 5 minutes in homogenizer, discharging is placed in the raw material of compound in double screw extruder and makes material, extruder temperature
Between 160 DEG C -180 DEG C, rotating speed is 200r/min for control.Batten is prepared, by corresponding standard testing（It is shown in Table 2）, performance knot
Fruit is shown in Table 3.
Table 1：Formula composition (part of embodiment 1-3）
Table 2：Mechanics Performance Testing standard
| Test event | Testing standard |
| Tensile strength MPa | GB/T 1040.1-2006 |
| Elongation at break % | GB/T 1040.1-2006 |
| Bending strength MPa | ASTM D-790 |
| Bending moduluses MPa | ASTM D-790 |
| The strong KJ/m of notch shock2 | GB/T 1043-93 |
Table 3：The Mechanics Performance Testing of POM feed backs in embodiment 1-3
| Test event | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Tensile strength MPa | 58 | 64 | 68 |
| Elongation at break % | 56% | 68% | 70% |
| Bending strength MPa | 80 | 85 | 90 |
| Bending moduluses MPa | 82 | 86 | 98 |
| The strong KJ/m of notch shock2 | 64 | 89 | 88 |
Comparative example 1-4, in each comparative example, the weight distribution ratio of each component is as shown in table 4.Each component is weighed by proportioning, Yu Gao
Fast stirrer for mixing 4 minutes, discharging is placed in the raw material of compound in double screw extruder makes material, the temperature 160 of extruder
DEG C -180 DEG C, rotating speed 150r/min.Batten is prepared, by corresponding standard testing（It is shown in Table 2）, results of property is shown in Table 5.
Table 4：The formula composition of comparative example 1-4
Table 5：The Mechanics Performance Testing of POM is reclaimed in comparative example 1-4
| Test event | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Tensile strength MPa | 58 | 64 | 68 | 80 |
| Elongation at break % | 56% | 68% | 70% | 69% |
| Bending strength MPa | 80 | 85 | 90 | 85 |
| Bending moduluses MPa | 82 | 86 | 98 | 79 |
| The strong KJ/m of notch shock2 | 64 | 89 | 88 | 96 |
From 3 embodiment 1-3 of table and the mechanical experimental results of comparative example 1-4, we understand：Use merely toughener
When, the tensile property of material can be reduced while improving and reclaiming POM impact properties；And obtained micro- crosslinking masterbatch
Particle diameter is put into after being crushed to 10～50 μm the twin-screw extrusion of big L/D ratio by crosslinking material and recovery POM, inorganic filler etc. again
Shear-mixed in machine, can also improve its tensile property while improving and reclaiming POM impact properties；Realize to reclaiming POM
Material carries out the effect of activeness and quietness simultaneously.Introducing containing L-POSS structure cross-linking agent simultaneously also has certain to the course of processing
Help, play efficient crosslinked action.
The present invention is further illustrated above by specific embodiment, but these embodiments are only exemplary
, any restriction is not constituted to protection scope of the present invention.It will be appreciated by those skilled in the art that in the spirit without departing from the present invention
In the case of protection domain, technical solutions and their implementation methods of the present invention can be carried out various equivalencings, modification or
Improve, these all should fall within the scope of protection of the present invention.Protection scope of the present invention is defined by appended claim.
Claims (8)
1. a kind of isomerism modified polyacetal of cross-linking agent containing L-POSS, it is characterised in that described L-POSS cross-linking agent is to adopt
The method reacted with silane compound with L-POSS, product is the derivant of silane；Its structure is：
；
Based on mass weight part, its component is isomerism modified polyacetal：
Reclaim 100 parts of polyformaldehyde；
10～30 parts of toughener；
10～30 parts of crosslinking masterbatch；
10～20 parts of inorganic filler；
3～20 parts of heat stabilizer.
2. one kind cross-linking agent containing L-POSS isomerism modified polyacetal according to claim 1, it is characterised in that described
Synthetic cross-linking agent includes two stages, is to form raw material first, next to that silane produces active site so as to draw under catalytic action
Enter L-POSS formation chemical reactions and prepare silane crosslinker containing L-POSS.
3. one kind cross-linking agent containing L-POSS isomerism modified polyacetal according to claim 1, it is characterised in that institute
Toughener is stated at least one in POM/POE, POM/EVA.
4. one kind cross-linking agent containing L-POSS isomerism modified polyacetal according to claim 1, it is characterised in that described
Crosslinking masterbatch are made up of A material B material and product three step part of water preparation；
A expects composition:Polyformaldehyde
The cross-linking agent of structure novel containing L-POSS
Initiator（Cumyl peroxide (DCP)）
B expects composition：Polyformaldehyde
Catalyst（Dibutyl tin laurate）
Antioxidant（Antioxidant 1010）
Produce water preparation composition：Acid and metal-oxide；The acid produced in water preparation is stearic acid, at least one in mineral acid；Metal oxygen
Compound is Zinc Oxide, at least one in stannum oxide.
5. one kind cross-linking agent containing L-POSS isomerism modified polyacetal according to claim 1, it is characterised in that described
Filler is Calcium Carbonate, at least one in Pulvis Talci.
6. one kind cross-linking agent containing L-POSS isomerism modified polyacetal according to claim 1, it is characterised in that described
Heat stabilizer is triphenyl phosphite.
7. a kind of isomerism modified polyacetal preparation method of cross-linking agent containing L-POSS, it is characterised in that methods described include with
Lower step：
A, 95 parts of A material is weighed by mass fraction, after 4.5 parts of B material mixing, is put into extruding pelletization in double screw extruder, then again with
0.5 part of product water preparation（Stearic acid and Zinc Oxide 1:1 mixture）Mix homogeneously is put into double screw extruder extruding pelletization and forms friendship
Connection masterbatch；
B, the micro- crosslinking masterbatch in A portions are first put into Universalpulverizer grinding are placed in planetary ball mill until crosslinking masterbatch
Particle diameter reach 10～50 μm till；
C, hard POM materials forced air drying 6～8 hours under the conditions of 80 DEG C will be reclaimed, by weight ratio by micro- crosslinking masterbatch, heat
Stabilizer, recovery hard POM, inorganic filler mix 4～6 minutes in putting into high-speed mixer so as to uniform to mix；
D, the material of the above-mentioned mix homogeneously in high-speed mixer is added to screw slenderness ratio for 36, rotating speed is 200r/min's
In double screw extruder, the mean diameter of micro- crosslinking masterbatch is controlled 10 using the Strong shear power of twin screw in the molten state
～50 μm, while crosslinking material is mixed homogeneously with heat stabilizer, reclaimed materials and inorganic filler, by above-mentioned compound extruding pelletization
Obtain the regeneration hard POM containing crosslinking POM.
8. one kind cross-linking agent containing L-POSS isomerism modified polyacetal preparation method according to claim 7, its feature
It is that the control of the extruder temperature of the double screw extruder is between 160 DEG C -180 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611223474.8A CN106589786B (en) | 2016-12-27 | 2016-12-27 | One kind isomerism modified polyacetal of crosslinking agent containing L-POSS and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611223474.8A CN106589786B (en) | 2016-12-27 | 2016-12-27 | One kind isomerism modified polyacetal of crosslinking agent containing L-POSS and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106589786A true CN106589786A (en) | 2017-04-26 |
| CN106589786B CN106589786B (en) | 2018-12-18 |
Family
ID=58602651
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611223474.8A Active CN106589786B (en) | 2016-12-27 | 2016-12-27 | One kind isomerism modified polyacetal of crosslinking agent containing L-POSS and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106589786B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112142979A (en) * | 2020-09-20 | 2020-12-29 | 南开大学 | Pyramid type polyoxometallate-cage type silsesquioxane hybrid molecule and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5623030A (en) * | 1994-12-01 | 1997-04-22 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Curable composition and process for producing molded articles using the same |
| CN1796441A (en) * | 2004-12-30 | 2006-07-05 | 中国科学院化学研究所 | Trapezoidal organic poly sesquisiloxane and preparation method |
| CN103657456A (en) * | 2013-12-18 | 2014-03-26 | 北京工商大学 | Preparation method of ethanol-permselective POSS (polyhedral oligomeric silsesquioxanes)/silicone rubber composite membrane |
| CN104903404A (en) * | 2013-01-09 | 2015-09-09 | 株式会社大赛璐 | Curable resin composition, and cured product of same |
-
2016
- 2016-12-27 CN CN201611223474.8A patent/CN106589786B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5623030A (en) * | 1994-12-01 | 1997-04-22 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Curable composition and process for producing molded articles using the same |
| CN1796441A (en) * | 2004-12-30 | 2006-07-05 | 中国科学院化学研究所 | Trapezoidal organic poly sesquisiloxane and preparation method |
| CN104903404A (en) * | 2013-01-09 | 2015-09-09 | 株式会社大赛璐 | Curable resin composition, and cured product of same |
| CN103657456A (en) * | 2013-12-18 | 2014-03-26 | 北京工商大学 | Preparation method of ethanol-permselective POSS (polyhedral oligomeric silsesquioxanes)/silicone rubber composite membrane |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112142979A (en) * | 2020-09-20 | 2020-12-29 | 南开大学 | Pyramid type polyoxometallate-cage type silsesquioxane hybrid molecule and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106589786B (en) | 2018-12-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103613883B (en) | A kind of take Graphene as Wear-resistant hard composite material of filler and preparation method thereof | |
| CN112724571B (en) | Regenerated alloy material based on chemical and physical common modification and preparation method thereof | |
| CN106751095B (en) | Isomerism containing L-POSS crosslinking agents is modified recycling PS and preparation method thereof | |
| CN109535681B (en) | Alloy material for high-fluidity thin-wall product and preparation method thereof | |
| CN102040817B (en) | Polycarbonate (PC)/poly ethylene (PE) plastic alloy as well as preparation method and application thereof | |
| CN106589786A (en) | L-POSS crosslinking agent contained isomerism modified polyformaldehyde and preparation method thereof | |
| CN106810743A (en) | PE and preparation method thereof is reclaimed in isomerism crosslinking toughness reinforcing enhancing | |
| CN105237996B (en) | Recycled polycarbonate reinforced and toughened through isomeric crosslinking method and preparation method of recycled polycarbonate | |
| CN106832893B (en) | A kind of isomerism recycling nylon of the crosslinking agent containing L-POSS and preparation method thereof | |
| CN105733231B (en) | With calcium sulfate whisker modified Polycarbonate alloy material and its preparation method | |
| CN113429807B (en) | Modified graphene and preparation method and application thereof | |
| CN108822396A (en) | A kind of regenerated plastics computer desk material and preparation method thereof | |
| CN107540978B (en) | A kind of conduction flame-proof PVC composition and preparation method thereof | |
| CN105237944B (en) | One kind reclaims polyformaldehyde and preparation method thereof with isomerism cross-linking method activeness and quietness | |
| CN112608540A (en) | Flame-retardant antistatic polyethylene for underground coal mine, and preparation method and application thereof | |
| CN106479134B (en) | A kind of isomerism cross-linking method of crosslinking agent containing L-POSS is modified polybutylene terephthalate (PBT)（PBT）And preparation method thereof | |
| CN106751710B (en) | A kind of isomerism MODIFIED PP O and preparation method thereof containing Sakyamuni, the founder of Buddhism's structure crosslinking agent | |
| CN106810832A (en) | Modified polyethylene terephthalate of isomerism containing condensed cyclic structure crosslinking agent and preparation method thereof | |
| CN106674522B (en) | Isomerism cross-linking method containing L-POSS crosslinking agents is modified recycling PC and preparation method thereof | |
| CN106832714A (en) | PMMA that a kind of activeness and quietness is reclaimed and preparation method thereof | |
| CN106832739B (en) | A kind of cross-linking modified recycling ABS preparation method of the isomerism of the crosslinking agent containing condensed cyclic structure | |
| CN1133693C (en) | Organic rigid-particle filled composite material and its preparation | |
| CN107043518B (en) | Isomerism containing L-POSS crosslinking agents is modified recycling PEEK and preparation method thereof | |
| CN106832894B (en) | A kind of isomerism of the crosslinking agent containing condensed cyclic structure is modified to recycle nylon and preparation method thereof | |
| CN114106550B (en) | Yellowing-resistant high-impact halogen-free flame-retardant PC material and preparation process thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |