CN101817840A - Silicic ester flame-retardant compound and preparation method thereof - Google Patents
Silicic ester flame-retardant compound and preparation method thereof Download PDFInfo
- Publication number
- CN101817840A CN101817840A CN201010184226A CN201010184226A CN101817840A CN 101817840 A CN101817840 A CN 101817840A CN 201010184226 A CN201010184226 A CN 201010184226A CN 201010184226 A CN201010184226 A CN 201010184226A CN 101817840 A CN101817840 A CN 101817840A
- Authority
- CN
- China
- Prior art keywords
- silicon tetrachloride
- reaction
- hours
- preparation
- nitrogen protection
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Abstract
The invention relates to a silicic ester flame-retardant compound and a preparation method thereof. The structure of the polymer is shown as the formula in the specification, wherein R' is oxygen, aryl or straight-chain or branched-chain alkyl having 1 to 9 carbon atoms, and R is aryl or straight-chain or branched-chain alkyl having 1 to 10 carbon atoms. The synthesis method comprises the following steps of: mixing silicon tetrachloride and the epoxy compound or the chlorohydrin corresponding to the epoxy compound in the presence of nitrogen protection and at initial temperature of 20 DEG C, and directly reacting under the heating condition; and then cooling, purifying and drying the reaction product to obtain the target product. The compound has stable physical/chemical performance and high flame retardancy as well as good compatibility with polymer substrate, and is safe and environment-friendly, diverse in process, easy to implement and suitable for manufacturers of various scales.
Description
Technical field
The present invention relates to a kind of silicon halogen cooperative flame retardant and preparation technology thereof, be specifically related to a kind of silicic ester flame-retardant compound compound and preparation method thereof, this compound can be used as the fire retardant or the softening agent of materials such as polyvinyl chloride, polyester, polyurethanes, Resins, epoxy, fiber glass resin, coating.
Background technology
China's solar-grade polysilicon industry (photovoltaic industry) has obtained developing rapidly at present, but the relevant auxiliary facility of this industry does not obtain synchronized development, and the waste material silicon tetrachloride that causes certainly leading in the solar-grade polysilicon industry production process can't be utilized effectively or handle.Because of the environmental pollution that can't handling of silicon tetrachloride causes has formed impassable obstacle for the polysilicon industry development.Add the pay attention to day by day of people, cause the handling problem of silicon tetrachloride to become the bottleneck problem that the restriction photovoltaic industry develops environmental protection.But meanwhile element silicon is also because of its unique thermostability, and good dispersiveness prevents that molten anti-drippage property becomes an important directions of current fire retardant development research.Yet, being aspect the fire retardant exploitation of raw material with the silicon tetrachloride, report is not arranged so far, directly limited the related industries development.Therefore, to the development research of silicon tetrachloride, aspects such as the fire retardant industry of China and photovoltaic industry had urgent realistic meaning and long-range strategic importance in flame retardant area.
Summary of the invention
One of purpose of the present invention is to propose a kind of silicic ester flame-retardant compound, and its synthesis technique is simple, and physical and chemical performance is stable, and the flame-retarded efficiency height is good with the macromolecular material intermiscibility, can overcome deficiency of the prior art.
For achieving the above object, the present invention has adopted following technical scheme:
A kind of silicic ester flame-retardant compound is characterized in that, the structure of this polymkeric substance is shown below:
Above-mentioned R ' is hydrogen, aryl or the straight or branched alkyl that contains 1～9 C atom, and R is hydrogen, aryl or the straight or branched alkyl that contains 1～10 C atom.
Another object of the present invention is to propose a kind of synthetic method of silicic ester flame-retardant compound, its technology is simple, is convenient to control, be easy to large-scale production, and raw material is cheap and easy to get, and equipment is simple, and is with low cost, and its technical scheme is as follows:
The preparation method of silicic ester flame-retardant compound is characterized in that as mentioned above, and this method is:
Under nitrogen protection, the chloro-hydrin(e) reaction that silicon tetrachloride and epoxy compounds or epoxy compounds hydrolyzable are generated is cooled off, is purified reaction product then, thereby obtains described silicon ester.
Particularly, this method is:
Under nitrogen protection; in 50～100 ℃ temperature range; making mol ratio is 1: 4～8 silicon tetrachloride and epoxy compounds direct reaction 4～8 hours; perhaps making mol ratio is 1: 4～8 the silicon tetrachloride chloro-hydrin(e) direct reaction corresponding with epoxy compounds 4～8 hours; then reaction product is cooled off, purified, thereby obtain described silicon ester.Further, this method is specially:
Under initial temperature is 20 ℃, the condition of nitrogen protection; the mol ratio of control silicon tetrachloride and propylene oxide is 1: 4～8; propylene oxide is added drop-wise in the silicon tetrachloride; the direct addition reaction; then slowly be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
Under initial temperature is 20 ℃, the condition of nitrogen protection; the mol ratio of control silicon tetrachloride and propylene oxide is 1: 4～8; silicon tetrachloride is added drop-wise to the propylene oxide under liquid level; the direct addition reaction; then slowly be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
This method also can be:
Under nitrogen protection; the mol ratio of control silicon tetrachloride and 2-propylene chlorohydrin is 1: 4～8; begin silicon tetrachloride is added drop-wise in the 2-propylene chlorohydrin at 20 ℃; direct reaction is emitted hydrogenchloride; then slowly be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
Under nitrogen protection; the mol ratio of control silicon tetrachloride and 2-propylene chlorohydrin is 1: 4～8; begin the 2-propylene chlorohydrin is added drop-wise in the silicon tetrachloride at 20 ℃; direct reaction is emitted hydrogenchloride; then slowly be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
Under nitrogen protection; the mol ratio of control silicon tetrachloride and 1-chlorine 2-propyl alcohol is 1: 4～8; begin silicon tetrachloride is added drop-wise in the 1-chlorine 2-propyl alcohol at 20 ℃; direct reaction is emitted hydrogenchloride; then slowly be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
Under nitrogen protection; the mol ratio of control silicon tetrachloride and 1-chlorine 2-propyl alcohol is 1: 4～8; begin 1-chlorine 2-propyl alcohol is added drop-wise in the silicon tetrachloride at 20 ℃; direct reaction is emitted hydrogenchloride; then slowly be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
Under nitrogen protection; the mol ratio of control silicon tetrachloride and butylene oxide ring is 1: 4～8; begin butylene oxide ring is added drop-wise in the silicon tetrachloride at 20 ℃; direct reaction; then slowly be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
Under nitrogen protection; the mol ratio of control silicon tetrachloride and butylene oxide ring is 1: 4～8; begin silicon tetrachloride is added drop-wise in the butylene oxide ring at 20 ℃; direct reaction; then slowly be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
Under nitrogen protection; the mol ratio of control silicon tetrachloride and 2-butylene-chlorohydrin is 1: 4～8; begin the 2-butylene-chlorohydrin is added drop-wise in the silicon tetrachloride at 20 ℃; direct reaction is emitted hydrogenchloride; then slowly be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
Under nitrogen protection; the mol ratio of control silicon tetrachloride and 1-chloro-2-butanols is 1: 4～8; begin 1-chloro-2-butanols is added drop-wise in the silicon tetrachloride at 20 ℃; hydrogenchloride is emitted in reaction; then slowly be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
Under nitrogen protection; the mol ratio of control silicon tetrachloride and phenyl ethylene oxide is 1: 4～8; begin phenyl ethylene oxide is added in the silicon tetrachloride at 20 ℃; the direct addition reaction; then slowly be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
Under nitrogen protection; the mol ratio of control silicon tetrachloride and 1-phenyl-ethylene chlorhydrin is 1: 4～8; begin 1-phenyl-ethylene chlorhydrin is added drop-wise in the silicon tetrachloride at 20 ℃; hydrogenchloride is emitted in reaction; then slowly be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
Under nitrogen protection; control silicon tetrachloride and 2-chloro-2-phenyl-alcoholic acid mol ratio are 1: 4～8; begin 2-chloro-2-phenyl-ethanol is added drop-wise in the silicon tetrachloride at 20 ℃; hydrogenchloride is emitted in reaction; then slowly be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
Described " slowly heating up " and " progressively improving temperature with reaction " are meant: because reaction is thermopositive reaction, and silicon tetrachloride boiling point (57.6 ℃) is lower, therefore, when reaction has just begun, escape for preventing the silicon tetrachloride boiling, it is low that temperature of reaction need be provided with, and along with constantly carrying out of reaction, the amount of lower boiling raw material silicon tetrachloride reduces gradually and improves temperature of reaction lentamente.
The detailed process that above-mentioned product carries out purification processes is: underpressure distillation steams excessive reactant, reclaims and uses, the neutralization washing, tell organic layer, organic layer is carried out underpressure distillation remove and to anhydrate and low boilers, thereby obtain silicic ester flame-retardant compound, excessive reactant can reclaim use.
Silicic acid four of the present invention (chloropropyl) ester flame-retardant compound is colourless or yellow liquid, and its decomposition temperature is 240 ± 5 ℃, and flash-point (open cup) is 212 ± 5 ℃, productive rate is 95%～99%, degree Beaume is 13.85 (9 ℃), and density is 1.113 (9 ℃), and refractive index is n
D 13=1.4536.
Silicic acid four of the present invention (chlorobutyl) ester flame-retardant compound is colourless or yellow liquid, and its decomposition temperature is 220 ± 5 ℃, and flash-point (open cup) is 205 ± 5 ℃, and productive rate is 95%～99%.
Silicic acid four of the present invention (phenyl-chloride ethyl) ester flame-retardant compound is colourless or yellow liquid, and its decomposition temperature is 292 ± 5 ℃, and flash-point (open cup) is 276 ± 5 ℃, and productive rate is 95%～99%.
It is suitable as the fire retardant or the softening agent of materials such as polyvinyl chloride, polyester, polyurethanes, Resins, epoxy, fiber glass resin, coating, and the synthesis technique principle of this silicic ester flame-retardant compound is shown below:
Perhaps
Compared with prior art, beneficial effect of the present invention is:
1. the present invention proposes silicate ester compound as fire retardant or softening agent, because silicon and carbon are congenerss, similar intermiscibility to macromolecular material of silicate ester compound and plasticity are good; Silicon halogen cooperative flame retardant usefulness height.
2. silicic ester flame-retardant compound of the present invention synthetic consumed the silicon tetrachloride that the polysilicon industry is given off, and helps environmental protection, and contains the element silicon better heat stability, so good prospects for application is arranged;
3. the synthesis technique of silicic ester flame-retardant compound of the present invention is single step reaction, and is simple and easy to control, need not the special reaction condition, and equipment is simple, and is with low cost, is suitable for large-scale production.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is described further.
Preparation example 1 is being equipped with agitator; thermometer; efficient reflux condensing tube and accurate the stirring in the 250ml four-hole bottle that seals; feed nitrogen protection; add the 0.1mol silicon tetrachloride; adorn the expansible soft seal cover that extremely to stretch in that prolong is suitable for reading; stir; 20 ℃ of beginning liquid levels drip the propylene oxide (progressively improving temperature with reaction) of 0.6mol down; slowly be warmed up to 50 ℃ then; the holding temperature reaction is after 8 hours, and underpressure distillation goes out excessive reactant recovery to be used, the neutralization washing; layering; separate the organic layer underpressure distillation and be silicic acid four (chloropropyl) ester, its productive rate is 99%, and decomposition temperature is 240 ± 5 ℃; flash-point (open cup) is 212 ± 5 ℃; degree Beaume is 13.85 (9 ℃), and density is 1.113 (9 ℃), and refractive index is n
D 13=1.4536.
Preparation example 2 is being equipped with agitator; thermometer; efficient reflux condensing tube and accurate the stirring in the 250ml four-hole bottle that seals; feed nitrogen protection; add the 0.1mol silicon tetrachloride; adorn the expansible soft seal cover that extremely to stretch in that prolong is suitable for reading; stir; 20 ℃ of beginning liquid levels drip the propylene oxide (progressively improving temperature with reaction) of 0.5mol down; slowly be warmed up to 60 ℃ then; the holding temperature reaction is after 7 hours, and underpressure distillation goes out excessive reactant recovery to be used, the neutralization washing; layering; separate the organic layer underpressure distillation and be silicic acid four (chloropropyl) ester, its productive rate is 97%, and decomposition temperature is 240 ± 5 ℃; flash-point (open cup) is 212 ± 5 ℃; degree Beaume is 13.85 (9 ℃), and density is 1.113 (9 ℃), and refractive index is n
D 13=1.4536.
Preparation example 3 is being equipped with agitator; thermometer; efficient reflux condensing tube and accurate the stirring in the 250ml four-hole bottle that seals; feed nitrogen protection; add the 0.1mol silicon tetrachloride; adorn an expansible soft seal cover of extremely to stretch and stir in that prolong is suitable for reading; 20 ℃ of beginning liquid levels drip the propylene oxide (progressively improving temperature with reaction) of 0.55mol down; slowly be warmed up to 70 ℃ then; the holding temperature reaction is after 6 hours; underpressure distillation goes out excessive reactant recovery and uses; the neutralization washing, layering separates the organic layer underpressure distillation and is silicic acid four (chloropropyl) ester; its productive rate is 99%; decomposition temperature is 240 ± 5 ℃, and flash-point (open cup) is 212 ± 5 ℃, and degree Beaume is 13.85 (9 ℃); density is 1.113 (9 ℃), and refractive index is n
D 13=1.4536.
Preparation example 4 is being equipped with agitator; thermometer; efficient reflux condensing tube and accurate the stirring in the 250ml four-hole bottle that seals; feed nitrogen protection; add the 0.1mol silicon tetrachloride; adorn the expansible soft seal cover that extremely to stretch in that prolong is suitable for reading; stir; 20 ℃ of beginning liquid levels drip the propylene oxide (progressively improving temperature with reaction) of 0.48mol down; slowly be warmed up to 80 ℃ then; the holding temperature reaction is after 5 hours, and underpressure distillation goes out excessive reactant recovery to be used, the neutralization washing; layering; separate the organic layer underpressure distillation and be silicic acid four (chloropropyl) ester, its productive rate is 98%, and decomposition temperature is 240 ± 5 ℃; flash-point (open cup) is 212 ± 5 ℃; degree Beaume is 13.85 (9 ℃), and density is 1.113 (9 ℃), and refractive index is n
D 13=1.4536.
Preparation example 5 is being equipped with agitator; thermometer; efficient reflux condensing tube and accurate the stirring in the 250ml four-hole bottle that seals; feed nitrogen protection; add the 0.1mol silicon tetrachloride; adorn the expansible soft seal cover that extremely to stretch in that prolong is suitable for reading; stir; 20 ℃ of beginning liquid levels drip the propylene oxide (progressively improving temperature with reaction) of 0.44mol down; slowly be warmed up to 90 ℃ then; the holding temperature reaction is after 4 hours, and underpressure distillation goes out excessive reactant recovery to be used, the neutralization washing; layering; separate the organic layer underpressure distillation and be silicic acid four (chloropropyl) ester, its productive rate is 96%, and decomposition temperature is 240 ± 5 ℃; flash-point (open cup) is 212 ± 5 ℃; degree Beaume is 13.85 (9 ℃), and density is 1.113 (9 ℃), and refractive index is n
D 13=1.4536.
Preparation example 6 is being equipped with agitator; thermometer; efficient reflux condensing tube and accurate the stirring in the 250ml four-hole bottle that seals; feed nitrogen protection; add the 0.1mol silicon tetrachloride; adorn the expansible soft seal cover that extremely to stretch in that prolong is suitable for reading; stir; 20 ℃ of beginning liquid levels drip the propylene oxide (progressively improving temperature with reaction) of 0.40mol down; slowly be warmed up to 100 ℃ then; the holding temperature reaction is after 4 hours, and underpressure distillation goes out excessive reactant recovery to be used, the neutralization washing; layering; separate the organic layer underpressure distillation and be silicic acid four (chloropropyl) ester, its productive rate is 95%, and decomposition temperature is 240 ± 5 ℃; flash-point (open cup) is 212 ± 5 ℃; degree Beaume is 13.85 (9 ℃), and density is 1.113 (9 ℃), and refractive index is n
D 13=1.4536.
Preparation example 7 is in being equipped with the 250ml there-necked flask of agitator and drying tube; feed nitrogen protection; the 2-propylene chlorohydrin that adds 0.80mol; stir; 20 ℃ drip 0.1mol silicon tetrachloride (progressively improving temperature with reaction); slowly be warmed up to 60 ℃ then; the holding temperature reaction is after 7 hours; underpressure distillation goes out excessive reactant to be reused, and the neutralization washing separates organic layer; underpressure distillation steams water and low boilers is silicic acid four (chloropropyl) ester; its productive rate is 97%, and decomposition temperature is 240 ± 5 ℃, and flash-point (open cup) is 212 ± 5 ℃.Degree Beaume is 13.85 (9 ℃), and density is 1.113 (9 ℃).
Preparation example 8 is in being equipped with the 250ml there-necked flask of agitator and drying tube; feed nitrogen protection; the 2-propylene chlorohydrin that adds 0.46mol; stir; 20 ℃ drip 0.1mol silicon tetrachloride (progressively improving temperature with reaction); slowly be warmed up to 80 ℃ then; the holding temperature reaction is after 6 hours; underpressure distillation goes out excessive reactant to be reused, and the neutralization washing separates organic layer; underpressure distillation steams water and low boilers is silicic acid four (chloropropyl) ester; its productive rate is 97%, and decomposition temperature is 240 ± 5 ℃, and flash-point (open cup) is 212 ± 5 ℃.Degree Beaume is 13.85 (9 ℃), and density is 1.113 (9 ℃).
Preparation example 9 is in being equipped with the 250ml there-necked flask of agitator and drying tube; feed nitrogen protection; the 2-propylene chlorohydrin that adds 0.42mol; stir; 20 ℃ drip 0.1mol silicon tetrachloride (progressively improving temperature with reaction); slowly be warmed up to 100 ℃ then; the holding temperature reaction is after 4 hours; underpressure distillation goes out excessive reactant to be reused, and the neutralization washing separates organic layer; underpressure distillation steams water and low boilers is silicic acid four (chloropropyl) ester; its productive rate is 96%, and decomposition temperature is 240 ± 5 ℃, and flash-point (open cup) is 212 ± 5 ℃.Degree Beaume is 13.85 (9 ℃), and density is 1.113 (9 ℃).
Preparation example 10 is equipped with in the 250ml there-necked flask of agitator and drying tube; feed nitrogen protection; the 1-chlorine 2-propyl alcohol that adds 0.48mol; stir; 20 ℃ drip 0.1mol silicon tetrachloride (progressively improving temperature with reaction); slowly be warmed up to 60 ℃ then; the holding temperature reaction is after 8 hours; underpressure distillation goes out excessive reactant to be reused, and the neutralization washing separates organic layer; underpressure distillation steams water and low boilers is silicic acid four (chloropropyl) ester; its productive rate is 95%, and decomposition temperature is 240 ± 5 ℃, and flash-point (open cup) is 212 ± 5 ℃.Degree Beaume is 13.85 (9 ℃), and density is 1.113 (9 ℃).
Preparation example 11 is in being equipped with the 250ml there-necked flask of agitator and drying tube; feed nitrogen protection; the 1-chlorine 2-propyl alcohol that adds 0.44mol; stir; 20 ℃ drip 0.1mol silicon tetrachloride (progressively improving temperature with reaction); slowly be warmed up to 80 ℃ then; the holding temperature reaction is after 6 hours; underpressure distillation goes out excessive reactant to be reused, and the neutralization washing separates organic layer; underpressure distillation steams water and low boilers is silicic acid four (chloropropyl) ester; its productive rate is 97%, and decomposition temperature is 240 ± 5 ℃, and flash-point (open cup) is 212 ± 5 ℃.Degree Beaume is 13.85 (9 ℃), and density is 1.113 (9 ℃).
Preparation example 12 is in being equipped with the 250ml there-necked flask of agitator and drying tube; feed nitrogen protection; the 1-chlorine 2-propyl alcohol that adds 0.4mol; stir; 20 ℃ drip 0.1mol silicon tetrachloride (progressively improving temperature with reaction); slowly be warmed up to 100 ℃ then; the holding temperature reaction is after 4 hours; underpressure distillation goes out excessive reactant to be reused, and the neutralization washing separates organic layer; underpressure distillation steams water and low boilers is silicic acid four (chloropropyl) ester; its productive rate is 95%, and decomposition temperature is 240 ± 5 ℃, and flash-point (open cup) is 212 ± 5 ℃.Degree Beaume is 13.85 (9 ℃), and density is 1.113 (9 ℃).
Preparation example 13 is being equipped with agitator; thermometer; efficient reflux condensing tube and accurate the stirring in the 250ml four-hole bottle that seals; feed nitrogen protection; add the 0.1mol silicon tetrachloride; adorn the expansible soft seal cover that extremely to stretch in that prolong is suitable for reading; stir; 20 ℃ of butylene oxide rings (progressively improving temperature) that begin to drip 0.6mol with reaction; slowly be warmed up to 80 ℃ then, the holding temperature reaction is after 7 hours, and underpressure distillation goes out excessive reactant and reuses; the neutralization washing; layering separates the organic layer underpressure distillation and is silicic acid four (chlorobutyl) ester, and its productive rate is 97%; decomposition temperature is 220 ± 5 ℃, and flash-point (open cup) is 205 ± 5 ℃.
Preparation example 14 is being equipped with agitator; thermometer; efficient reflux condensing tube and accurate the stirring in the 250ml four-hole bottle that seals; feed nitrogen protection; the butylene oxide ring that adds 0.5mol; adorn the expansible soft seal cover that extremely to stretch in that prolong is suitable for reading; stir; 20 ℃ begin to drip 0.1mol silicon tetrachloride (progressively improving temperature with reaction); slowly be warmed up to 80 ℃ then, the holding temperature reaction is after 7 hours, and underpressure distillation goes out excessive reactant and reuses; the neutralization washing; layering separates the organic layer underpressure distillation and is silicic acid four (chlorobutyl) ester, and its productive rate is 96%; decomposition temperature is 220 ± 5 ℃, and flash-point (opening cup) is 205 ± 5 ℃.
Preparation example 15 is being equipped with agitator; thermometer; efficient reflux condensing tube and accurate the stirring in the 250ml four-hole bottle that seals; feed nitrogen protection; add the 0.1mol silicon tetrachloride; adorn the expansible soft seal cover that extremely to stretch in that prolong is suitable for reading; stir; 20 ℃ of phenyl ethylene oxides (progressively improving temperature) that begin to drip 0.5mol with reaction; slowly be warmed up to 80 ℃ then, the holding temperature reaction is after 7 hours, and underpressure distillation goes out excessive reactant and reuses; the neutralization washing; layering separates the organic layer underpressure distillation and is silicic acid four (phenyl-chloride ethyl) ester, and its productive rate is 98%; decomposition temperature is 292 ± 5 ℃, and flash-point (open cup) is 276 ± 5 ℃.
Preparation example 16 is being equipped with agitator; thermometer; efficient reflux condensing tube and accurate the stirring in the 250ml four-hole bottle that seals; feed nitrogen protection; add the 0.1mol silicon tetrachloride; adorn the expansible soft seal cover that extremely to stretch in that prolong is suitable for reading; stir; 20 ℃ of 1-phenyl-ethylene chlorhydrins (progressively improving temperature) that begin to drip 0.48mol with reaction; slowly be warmed up to 90 ℃ then; the holding temperature reaction is after 8 hours; underpressure distillation goes out excessive reactant and reuses; the neutralization washing; layering separates the organic layer underpressure distillation and is silicic acid four (phenyl-chloride ethyl) ester, and its productive rate is 97%; decomposition temperature is 292 ± 5 ℃, and flash-point (open cup) is 276 ± 5 ℃.
Preparation example 17 is being equipped with agitator; thermometer; efficient reflux condensing tube and accurate the stirring in the 250ml four-hole bottle that seals; feed nitrogen protection; add the 0.1mol silicon tetrachloride; adorn the expansible soft seal cover that extremely to stretch in that prolong is suitable for reading; stir; 20 ℃ of 2-chloro-2-phenyl-ethanol (progressively improving temperature) that begin to drip 0.44mol with reaction; slowly be warmed up to 90 ℃ then; the holding temperature reaction is after 7 hours; underpressure distillation goes out excessive reactant and reuses; the neutralization washing, layering separates the organic layer underpressure distillation and is silicic acid four (phenyl-chloride ethyl) ester; its productive rate is 96%; decomposition temperature is 292 ± 5 ℃, and flash-point (open cup) is 276 ± 5 ℃.
Table 1
| Silicon tetrachloride | Active epoxy based compound or chloro-hydrin(e) | Temperature | Reaction times | Productive rate | |
| Preparation example 1 | ??0.1mol | Propylene oxide 0.6mol | ??50℃ | 8 hours | ??99％ |
| Preparation example 2 | ??0.1mol | Propylene oxide 0.5mol | ??60℃ | 7 hours | ??97％ |
| Preparation example 3 | ??0.1mol | Propylene oxide 0.55mol | ??70℃ | 6 hours | ??99％ |
| Preparation example 4 | ??0.1mol | Propylene oxide 0.48mol | ??80℃ | 5 hours | ??98％ |
| Preparation example 5 | ??0.1mol | Propylene oxide 0.44mol | ??90℃ | 4 hours | ??96％ |
| Preparation example 6 | ??0.1mol | Propylene oxide 0.40mol | ??100℃ | 4 hours | ??95％ |
| Preparation example 7 | ??0.1mol | 2-propylene chlorohydrin 0.80mol | ??60℃ | 7 hours | ??97％ |
| Preparation example 8 | ??0.1mol | 2-propylene chlorohydrin 0.46mol | ??80℃ | 6 hours | ??97％ |
| Preparation example 9 | ??0.1mol | 2-propylene chlorohydrin 0.42mol | ??100℃ | 4 hours | ??96％ |
| Preparation example 10 | ??0.1mol | 1-chlorine 2-propyl alcohol 0.48mol | ??60℃ | 8 hours | ??95％ |
| Preparation example 11 | ??0.1mol | 1-chlorine 2-propyl alcohol 0.44mol | ??80℃ | 6 hours | ??97％ |
| Preparation example 12 | ??0.1mol | 1-chlorine 2-propyl alcohol 0.4mol | ??100℃ | 4 hours | ??95％ |
| Silicon tetrachloride | Active epoxy based compound or chloro-hydrin(e) | Temperature | Reaction times | Productive rate | |
| Preparation example 13 | ??0.1mol | Butylene oxide ring 0.60mol | ??80℃ | 7 hours | ??97％ |
| Preparation example 14 | ??0.1mol | Butylene oxide ring 0.50mol | ??80℃ | 7 hours | ??96％ |
| Preparation example 15 | ??0.1mol | Phenyl ethylene oxide 0.5mol | ??80℃ | 7 hours | ??98％ |
| Preparation example 16 | ??0.1mol | 1-phenyl-ethylene chlorhydrin 0.48mol | ??90℃ | 8 hours | ??97％ |
| Preparation example 17 | ??0.1mol | 2-chloro-2-phenyl-ethanol 0.44mol | ??90℃ | 7 hours | ??96％ |
This case contriver also is applied to above-mentioned synthetic silicic ester flame-retardant compound in the polyvinyl chloride.Reference: GB/T2406-2008 " plastics combustibility test method-oxygen index method " surveys the flame retardant properties of product in polyvinyl chloride.Get the product silicic ester flame-retardant compound, plasticizer phthalic acid succinate, synergistic flame retardant antimonous oxide and polyvinyl chloride grind in varing proportions, mixing the back extrudes with forcing machine, and make long 15cm, diameter is the batten of 3mm and its flame retardant properties is tested that test-results is as shown in the table:
Table 2
| Embodiment | ??1 | ??2 | ??3 | ??4 | ??5 | ??6 | ??7 | ??9 | ??10 | ??11 |
| ??PVC | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 |
| The phthalic acid succinate | ??40 | ??40 | ??40 | ??40 | ??100 | |||||
| Silicic ester flame-retardant compound | ??10 | ??15 | ??20 | ??40 | ??100 | ??40 | ??100 | |||
| The trichlorine propyl phosphate | ??100 | |||||||||
| Antimonous oxide | ??5 | ??7.5 | ??10 | ??20 | ??50 | ??5 | ??5 | |||
| Oxygen index | ??31 | ??32 | ??31 | ??36 | ??30 | ??34 | ??29 | ??28 | ??25 | ??22 |
General, oxygen index reaches 27 just can think that its flame retardant properties is better.As seen from the above table, used the polyvinyl chloride of silicic acid four (two chloropropyls) ester to have excellent flame-retardant.Compare with fire retardant trichlorine propyl phosphate commonly used, silicic acid four (two chloropropyls) ester is better fire retardant.
Claims (20)
1. a silicic ester flame-retardant compound is characterized in that, the structure of this polymkeric substance is shown below:
Above-mentioned R ' is hydrogen, aryl or the straight or branched alkyl that contains 1～9 carbon atom, and R is hydrogen, aryl or the straight or branched alkyl that contains 1～10 carbon atom.
2. the preparation method of silicic ester flame-retardant compound according to claim 1 is characterized in that this method is:
Under nitrogen protection, the chloro-hydrin(e) reaction that silicon tetrachloride and epoxy compounds or epoxy compounds hydrolyzable are generated is cooled off, is purified reaction product then, thereby obtains described silicon ester.
3. the preparation method of silicic ester flame-retardant compound as claimed in claim 2 is characterized in that:
Described epoxy compounds is
Its pairing chloro-hydrin(e) is
Wherein, R ' is hydrogen, aryl or the straight or branched alkyl that contains 1～9 carbon atom, and R is hydrogen, aryl or the straight or branched alkyl that contains 1～10 carbon atom.
4. preparation method as claimed in claim 3, wherein, described epoxy compounds is selected from propylene oxide, butylene oxide ring, phenyl ethylene oxide; The chloro-hydrin(e) of described epoxy compounds correspondence is selected from 2-propylene chlorohydrin, 1-chloro-2-propanol, 2-butylene-chlorohydrin, 1-chloro-2-butanols, 1-phenyl-ethylene chlorhydrin, 2-chloro-2-phenyl-ethanol.
5. as each described preparation method of claim 2～4, it is characterized in that this method is:
Under nitrogen protection; in 50～100 ℃ temperature range; making mol ratio is 1: 4～8 silicon tetrachloride and epoxy compounds direct reaction 4～8 hours; perhaps making mol ratio is 1: 4～8 the silicon tetrachloride chloro-hydrin(e) direct reaction corresponding with epoxy compounds 4～8 hours; then reaction product is cooled off, purified, thereby obtain described silicon ester.
6. preparation method as claimed in claim 3 is characterized in that:
Under initial temperature is 20 ℃, the condition of nitrogen protection; the mol ratio of control silicon tetrachloride and propylene oxide is 1: 4～8; propylene oxide is added drop-wise in the silicon tetrachloride; the direct addition reaction; then be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
7. preparation method as claimed in claim 3 is characterized in that:
Under initial temperature is 20 ℃, the condition of nitrogen protection; the mol ratio of control silicon tetrachloride and propylene oxide is 1: 4～8; silicon tetrachloride is added drop-wise to the propylene oxide under liquid level; the direct addition reaction; then be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
8. preparation method as claimed in claim 3 is characterized in that:
Under nitrogen protection; the mol ratio of control silicon tetrachloride and 2-propylene chlorohydrin is 1: 4～8; begin silicon tetrachloride is added drop-wise in the 2-propylene chlorohydrin at 20 ℃; direct reaction is emitted hydrogenchloride; then be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
9. preparation method as claimed in claim 3 is characterized in that:
Under nitrogen protection; the mol ratio of control silicon tetrachloride and 2-propylene chlorohydrin is 1: 4～8; begin the 2-propylene chlorohydrin is added drop-wise in the silicon tetrachloride at 20 ℃; direct reaction is emitted hydrogenchloride; then be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
10. preparation method as claimed in claim 3 is characterized in that:
Under nitrogen protection; the mol ratio of control silicon tetrachloride and 1-chlorine 2-propyl alcohol is 1: 4～8; begin silicon tetrachloride is added drop-wise in the 1-chlorine 2-propyl alcohol at 20 ℃; direct reaction is emitted hydrogenchloride; then be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
11. preparation method as claimed in claim 3 is characterized in that:
Under nitrogen protection; the mol ratio of control silicon tetrachloride and 1-chlorine 2-propyl alcohol is 1: 4～8; begin 1-chlorine 2-propyl alcohol is added drop-wise in the silicon tetrachloride at 20 ℃; direct reaction is emitted hydrogenchloride; then be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
12. preparation method as claimed in claim 3 is characterized in that:
Under nitrogen protection; the mol ratio of control silicon tetrachloride and butylene oxide ring is 1: 4～8; begin butylene oxide ring is added drop-wise in the silicon tetrachloride at 20 ℃; direct reaction; then be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
13. preparation method as claimed in claim 3 is characterized in that:
Under nitrogen protection; the mol ratio of control silicon tetrachloride and butylene oxide ring is 1: 4～8; begin silicon tetrachloride is added drop-wise in the butylene oxide ring at 20 ℃; direct reaction; then be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
14. preparation method as claimed in claim 3 is characterized in that:
Under nitrogen protection; the mol ratio of control silicon tetrachloride and 2-butylene-chlorohydrin is 1: 4～8; begin the 2-butylene-chlorohydrin is added drop-wise in the silicon tetrachloride at 20 ℃; direct reaction is emitted hydrogenchloride; then be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
15. preparation method as claimed in claim 3 is characterized in that:
Under nitrogen protection; the mol ratio of control silicon tetrachloride and 1-chloro-2-butanols is 1: 4～8; begin 1-chloro-2-butanols is added drop-wise in the silicon tetrachloride at 20 ℃; hydrogenchloride is emitted in reaction; then be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
16. preparation method as claimed in claim 3 is characterized in that:
Under nitrogen protection; the mol ratio of control silicon tetrachloride and phenyl ethylene oxide is 1: 4～8; begin phenyl ethylene oxide is added in the silicon tetrachloride at 20 ℃; the direct addition reaction; then be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
17. preparation method as claimed in claim 3 is characterized in that:
Under nitrogen protection; the mol ratio of control silicon tetrachloride and 1-phenyl-ethylene chlorhydrin is 1: 4～8; begin 1-phenyl-ethylene chlorhydrin is added drop-wise in the silicon tetrachloride at 20 ℃; hydrogenchloride is emitted in reaction; then be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
18. preparation method as claimed in claim 3 is characterized in that:
Under nitrogen protection; control silicon tetrachloride and 2-chloro-2-phenyl-alcoholic acid mol ratio are 1: 4～8; begin 2-chloro-2-phenyl-ethanol is added drop-wise in the silicon tetrachloride at 20 ℃; hydrogenchloride is emitted in reaction; then be warming up to 50 ℃～100 ℃ sustained reactions 4～8 hours; then reaction product is purified, make silicic ester flame-retardant compound.
19., it is characterized in that reaction need not solvent as each described preparation method in the claim 2,5～18.
20. as each described preparation method in the claim 2,5～19, wherein, described purification steams excessive reactant for underpressure distillation, neutralization washing again, tell organic layer, organic layer is carried out underpressure distillation remove and to anhydrate and low boilers, thereby obtain silicic ester flame-retardant compound, excessive reactant can reclaim use.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010184226.3A CN101817840B (en) | 2010-05-27 | 2010-05-27 | Silicic ester flame-retardant compound and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010184226.3A CN101817840B (en) | 2010-05-27 | 2010-05-27 | Silicic ester flame-retardant compound and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101817840A true CN101817840A (en) | 2010-09-01 |
| CN101817840B CN101817840B (en) | 2014-02-05 |
Family
ID=42653132
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010184226.3A Active CN101817840B (en) | 2010-05-27 | 2010-05-27 | Silicic ester flame-retardant compound and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101817840B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010521A (en) * | 2010-11-01 | 2011-04-13 | 苏州科技学院 | Silicate ester flame-retardant plasticizer and preparation method thereof |
| CN102050961A (en) * | 2010-11-01 | 2011-05-11 | 苏州科技学院 | Aryl silicate ester flame retardant plasticizer and preparation method thereof |
| CN102731547A (en) * | 2012-07-17 | 2012-10-17 | 苏州科技学院 | Tetra-(tribromophenoxy chloropropyl) silicate fire retardant compound and preparation method thereof |
| CN102731546A (en) * | 2012-07-17 | 2012-10-17 | 苏州科技学院 | Flame retardant trichloroethyltribromophenoxychloropropylsilicate ester compound and preparation method thereof |
| CN102731553A (en) * | 2012-07-17 | 2012-10-17 | 苏州科技学院 | Tris(dichloropropyl) tribromophenoxy chloropropyl silicate compound and preparation method thereof |
| CN102731552A (en) * | 2012-07-17 | 2012-10-17 | 苏州科技学院 | Flame retardant tribromophenoxychloropropoxytri(chloropropyl) silicate compound and preparation method thereof |
| CN109111595A (en) * | 2018-07-21 | 2019-01-01 | 扬州工业职业技术学院 | A kind of novel silicon-series five-retardant and the preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2381137A (en) * | 1942-05-14 | 1945-08-07 | Gen Electric | Process of preparing tetrakis-2-chloroethyl silicate |
| US2813839A (en) * | 1951-06-13 | 1957-11-19 | Montclair Res Corp | Method of producing foams from self-frothing silicon resins |
| US3342898A (en) * | 1963-05-13 | 1967-09-19 | Diamond Alkali Co | Composition and process |
-
2010
- 2010-05-27 CN CN201010184226.3A patent/CN101817840B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2381137A (en) * | 1942-05-14 | 1945-08-07 | Gen Electric | Process of preparing tetrakis-2-chloroethyl silicate |
| US2813839A (en) * | 1951-06-13 | 1957-11-19 | Montclair Res Corp | Method of producing foams from self-frothing silicon resins |
| US3342898A (en) * | 1963-05-13 | 1967-09-19 | Diamond Alkali Co | Composition and process |
Non-Patent Citations (2)
| Title |
|---|
| 《J. Am. Chem. Soc.》 19450930 ROBERT O. SAUER, et al. Derivatives of the Methylchlorosilanes. II. 2-Chloroethoxysilanes 第1548-1549页 1-5,8-11,14-15,17-20 第67卷, 第9期 2 * |
| 《STN REGISTRY》 19841116 ACS RN: 18027-78-6 第1页结构式 1 , 2 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010521A (en) * | 2010-11-01 | 2011-04-13 | 苏州科技学院 | Silicate ester flame-retardant plasticizer and preparation method thereof |
| CN102050961A (en) * | 2010-11-01 | 2011-05-11 | 苏州科技学院 | Aryl silicate ester flame retardant plasticizer and preparation method thereof |
| CN102050961B (en) * | 2010-11-01 | 2012-10-10 | 苏州科技学院 | Aryl silicate ester flame retardant plasticizer and preparation method thereof |
| CN102010521B (en) * | 2010-11-01 | 2013-04-03 | 苏州科技学院 | Silicate ester flame-retardant plasticizer and preparation method thereof |
| CN102731552A (en) * | 2012-07-17 | 2012-10-17 | 苏州科技学院 | Flame retardant tribromophenoxychloropropoxytri(chloropropyl) silicate compound and preparation method thereof |
| CN102731553A (en) * | 2012-07-17 | 2012-10-17 | 苏州科技学院 | Tris(dichloropropyl) tribromophenoxy chloropropyl silicate compound and preparation method thereof |
| CN102731546A (en) * | 2012-07-17 | 2012-10-17 | 苏州科技学院 | Flame retardant trichloroethyltribromophenoxychloropropylsilicate ester compound and preparation method thereof |
| CN102731547A (en) * | 2012-07-17 | 2012-10-17 | 苏州科技学院 | Tetra-(tribromophenoxy chloropropyl) silicate fire retardant compound and preparation method thereof |
| CN102731547B (en) * | 2012-07-17 | 2015-03-04 | 苏州科技学院 | Tetra-(tribromophenoxy chloropropyl) silicate fire retardant compound and preparation method thereof |
| CN102731552B (en) * | 2012-07-17 | 2015-03-04 | 苏州科技学院 | Flame retardant tribromophenoxychloropropoxytri(chloropropyl) silicate compound and preparation method thereof |
| CN102731546B (en) * | 2012-07-17 | 2015-03-04 | 苏州科技学院 | Flame retardant trichloroethyltribromophenoxychloropropylsilicate ester compound and preparation method thereof |
| CN102731553B (en) * | 2012-07-17 | 2015-03-04 | 苏州科技学院 | Tris(dichloropropyl) tribromophenoxy chloropropyl silicate compound and preparation method thereof |
| CN109111595A (en) * | 2018-07-21 | 2019-01-01 | 扬州工业职业技术学院 | A kind of novel silicon-series five-retardant and the preparation method and application thereof |
| CN109111595B (en) * | 2018-07-21 | 2021-04-23 | 扬州工业职业技术学院 | Novel silicon-based flame retardant and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101817840B (en) | 2014-02-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102050961B (en) | Aryl silicate ester flame retardant plasticizer and preparation method thereof | |
| CN101817840B (en) | Silicic ester flame-retardant compound and preparation method thereof | |
| CN101830923B (en) | Silicic acid tetra (dichloropropyl) ester compound and preparation method thereof | |
| CN101817841B (en) | Tetra-(chloroethyl) silicate compound and preparation method thereof | |
| CN102731825B (en) | Chloro- and bromo-containing silicate flame retardant compound and preparation method thereof | |
| CN102140115B (en) | Flame-retardant plasticizer of methyl silicate trichloroethyl ester compound and preparation method thereof | |
| CN102731550B (en) | Triazinetrichloropropyl silicate compound and preparation method thereof | |
| CN102731548B (en) | Triazine chloro-trissilicate compound and preparation method thereof | |
| CN102010521B (en) | Silicate ester flame-retardant plasticizer and preparation method thereof | |
| CN102167707B (en) | Retardant plasticizer methyl silicate ester compound and preparation method thereof | |
| CN102731826B (en) | Halogenated tetra-aryl silicic acid ester compound serving as flame retardant and preparation method thereof | |
| CN102153780B (en) | Chlorine-containing methyl silicate flame retardant and preparation method thereof | |
| CN102731829B (en) | Novel silicon halide synergized disilicate flame retardant compound and preparation method thereof | |
| CN104693228A (en) | Flame retardant dibenzyl dimethylsilicate compound and preparation method thereof | |
| CN102140112B (en) | Halogenated organic silicate ester flame-retardant plasticizer compound and preparation method thereof | |
| CN102731547B (en) | Tetra-(tribromophenoxy chloropropyl) silicate fire retardant compound and preparation method thereof | |
| CN103333192B (en) | A kind of fire retardant three (tribromophenoxy) halogen npropoxysilane compound and preparation method thereof | |
| CN103554155A (en) | Flame retardant tris(hydroxyethyl) isocyanurate trisilicate ethyl chloride compound and preparation method thereof | |
| CN103333194B (en) | A kind of fire retardant silicic acid three (tribromo phenyl) (chloroethyl) compound and preparation method thereof | |
| CN104744504B (en) | A kind of silicon, nitrogen, the preparation method of halogen multielement cooperative flame retardant immunomodulator compounds | |
| CN104710454B (en) | Dimethyl silicic acid two (2,4,6- tribromophenoxies chloropropyl) ester compounds and preparation method thereof | |
| CN109824732A (en) | Fire-retardant carbon forming agent four (phosphono heterocycle shape esters of silicon acis methoxyl group) silane compound and preparation method thereof | |
| CN103554166A (en) | Flame retardant ethylenedioxy dual-silicate ethyl chloride compound and preparation method thereof | |
| CN104725413A (en) | Flame-retardant plasticizer propyl halogen dimethylsilicate compound and preparation method thereof | |
| CN103554159A (en) | Flame retardant ethylenedioxy dibromo-propyl bisilicate compound and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201124 Address after: No.78 Nanjing Road, Sijia Town, Haimen District, Nantong City, Jiangsu Province, 226100 Patentee after: Gaorun New Material Science and Technology (Nantong) Co.,Ltd. Address before: 215009 Suzhou high tech Zone, Jiangsu Province, School of chemistry, Suzhou University of Science and Technology Patentee before: Wang Yanlin |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220930 Address after: Group 18, Huolong Village, Sijia Town, Haimen District, Nantong City, Jiangsu Province 226100 Patentee after: Nantong Chushun Culture Communication Co.,Ltd. Address before: 226100 No.78 Nanjing Road, Sijia Town, Haimen District, Nantong City, Jiangsu Province Patentee before: Gaorun New Material Science and Technology (Nantong) Co.,Ltd. |
|
| TR01 | Transfer of patent right |