TWI688585B - Flame-retardant thermoplastic silicone vulcanizate and preparation method thereof - Google Patents

Abstract

The present disclosure provides a method for flame-retardant thermoplastic silicone vulcanizate. The method includes following steps: providing a synthetic material of flame-retardant thermoplastic polyurethane, performing a prepolymer synthesis step, and performing a dynamic vulcanization step. The synthetic material of flame-retardant thermoplastic polyurethane includes polyisocyanate compound, macromolecule polyol compound, and micromolecule polyol. The prepolymer synthesis step is for providing a flame-retardant thermoplastic silicone vulcanizate prepolymer. The dynamic vulcanization step is for providing a flame-retardant thermoplastic silicone vulcanizate. Accordingly, the flame-retardant thermoplastic silicone vulcanizate of the present disclosure has excellent flexibility, permanent flame-retardant, permanent weatherability, smooth, and abrasive resistance.

Description

Flame-retardant silicon-based thermoplastic vulcanizate and its synthesis method

The invention relates to a flame-retardant silicon-based thermoplastic vulcanizate and its synthesis method, in particular to a halogen-free flame-retardant silicon-based thermoplastic vulcanizate and its synthesis method.

In recent years, the application market of silicon-based thermoplastic vulcanizate (TPSiV) has become increasingly widespread. Its advantages are the fusion of the performance advantages of thermoplastic polyurethane and silicone materials, with excellent wear resistance, silky touch, lower than The surface friction coefficient of thermoplastic polyurethane, excellent adhesion with PC, PC/ABS, ABS and other resins, can still maintain high physical and mechanical properties after hot air aging, and is easy to extrude and injection molding. The disadvantage of thermoplastic vulcanizates is that they do not have flame retardant properties, making their applications limited.

However, the conventional thermoplastic polyurethane rubber (TPU) itself does not have flame retardant properties, but some related companies use halogenated flame retardants to add to the thermoplastic polyurethane rubber to improve its flame retardant performance. The advantages of halogenated flame retardants are good flame retardant effect, less dosage, less influence on material properties and excellent price, but the polymer materials containing halogenated flame retardants will produce a lot when pyrolysis or burning The smoke and corrosive gases cause pollution to the environment, and the related industry is bound to find other flame retardants to replace halogen flame retardants.

In view of this, how to synthesize a flame-retardant silicon-based thermoplastic vulcanizate and reduce the pollution caused to the environment, and can be widely used in a variety of industrial products, has become the goal of the relevant industry efforts.

An object of the present invention is to provide a method for synthesizing a flame-retardant silicon-based thermoplastic vulcanizate, based on a synthetic raw material of halogen-free flame-retardant thermoplastic polyurethane, and adding a silicon-containing compound to perform dynamic vulcanization to achieve a condensation reaction , Synthesize a flame-retardant silicon-based thermoplastic vulcanizate.

Another object of the present invention is to provide a flame-retardant silicon-based thermoplastic vulcanizate, which has the characteristics of permanent weather resistance, slippery feeling and permanent pseudo wear resistance, and the use of halogen-free flame retardants can reduce the occurrence of combustion A large amount of poisonous gas improves the environmental protection effect and is beneficial to expanding its application range.

One embodiment of the present invention is to provide a method for synthesizing a flame-retardant silicon-based thermoplastic vulcanizate, which includes providing a flame-retardant thermoplastic polyurethane synthetic raw material, performing a prepolymer synthesis step, and performing a dynamic vulcanization step. Among them, the aforementioned flame-retardant thermoplastic polyurethane synthetic raw materials include polyisocyanate compounds, macromolecular polyol compounds and small molecule polyols. The aforementioned prepolymer synthesis step is to add a silicone rubber base compound to the flame-retardant thermoplastic polyurethane synthesis raw material and mix it under a high-speed shearing device to obtain a silicone-based thermoplastic vulcanizate prepolymer. Finally, the aforementioned dynamic vulcanization step is to put the silicon-based thermoplastic vulcanizate prepolymer into a twin-screw extruder and add A silicone rubber hardener compound is added to melt-blend the silicone-based thermoplastic vulcanizate prepolymer and the silicone rubber hardener compound, and then dynamically vulcanized to achieve a condensation reaction to synthesize the flame-retardant silicone-based thermoplastic Vulcanized rubber.

According to the synthesis method of the flame-retardant silicon-based thermoplastic vulcanizate according to the foregoing embodiment, wherein the flame-retardant thermoplastic polyurethane synthetic raw material is used to synthesize a flame-retardant thermoplastic polyurethane polymer, and the flame-retardant thermoplastic polyurethane polymer may be It is polyester polyurethane, polyether polyurethane, polycarbonate polyurethane or blends thereof.

The method for synthesizing a flame-retardant silicon-based thermoplastic vulcanizate according to the foregoing embodiment, wherein the total weight of the polyisocyanate compound is 100 parts by weight, and the content of the macromolecular polyol compound may be 5 parts by weight to 100 The content of the small molecule polyol may be 5 parts by weight to 100 parts by weight.

其中，R為氫原子、氫氧基或碳數1至9的烷基，R,,為式(2)或式(3)所示之一結構：

其中，R_x為碳數1至4的烷基或苯基。 According to the synthesis method of the flame-retardant silicon-based thermoplastic vulcanizate according to the foregoing embodiment, wherein the small molecule polyol may further comprise a flame-retardant polyol, which has a structure as shown in formula (1):

Wherein, R is a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 9 carbon atoms, and R, is one of the structures shown in formula (2) or formula (3):

Here, R _x is an alkyl group having 1 to 4 carbon atoms or a phenyl group.

According to the synthesis method of the flame-retardant silicon-based thermoplastic vulcanizate according to the foregoing embodiment, wherein the flame-retardant polyol may be a diol of the DOPO series and has the formula (4), formula (5) or formula ( 6) One of the structures shown:

According to the synthesis method of the flame-retardant silicon-based thermoplastic vulcanizate according to the foregoing embodiment, wherein the silicone rubber base compound may be a diorganopolysiloxane fluid or resin.

According to the method for synthesizing a flame-retardant silicon-based thermoplastic vulcanizate according to the foregoing embodiment, wherein the silicone rubber base compound may be dimethyl siloxane monomer.

According to the method for synthesizing a flame-retardant silicon-based thermoplastic vulcanizate according to the aforementioned embodiment, the silicone rubber hardener compound may contain an organic hydrogenated silicon crosslinking agent.

According to the method for synthesizing a flame-retardant silicon-based thermoplastic vulcanizate according to the foregoing embodiment, the silicone rubber hardener may be dimethyl siloxane monomer.

According to the synthesis method of the flame-retardant silicon-based thermoplastic vulcanizate according to the foregoing embodiment, wherein the total weight of the polyisocyanate compound is 100 parts by weight, and the content of the silicone rubber base compound may be 2 parts by weight to 50 The content of the silicone rubber hardener compound may be 2 to 50 parts by weight.

According to the synthesis method of the flame-retardant silicon-based thermoplastic vulcanizate according to the foregoing embodiment, wherein the dynamic vulcanization step may further include adding a filler, and the filler may be diorganopolysiloxane or silicone resin.

According to the synthesis method of the flame-retardant silicon-based thermoplastic vulcanizate according to the foregoing embodiment, the filler may further include a reinforced filler of diorganopolysiloxane.

According to the method for synthesizing a flame-retardant silicon-based thermoplastic vulcanizate according to the foregoing embodiment, wherein the dynamic vulcanization step may further include adding a catalyst, and the catalyst is used to catalyze the condensation reaction.

According to the synthesis method of the flame-retardant silicon-based thermoplastic vulcanizate according to the foregoing embodiment, wherein the total weight of the polyisocyanate compound is 100 parts by weight, the content of the catalyst may be 0.01 parts by weight to 2 parts by weight.

Another embodiment of the present invention is to provide a flame-retardant silicon-based thermoplastic vulcanizate, which is synthesized by the aforementioned synthesis method.

The flame-retardant silicon-based thermoplastic vulcanizate according to the foregoing embodiment, wherein the flame-retardant silicon-based thermoplastic vulcanizate may have an oxygen limiting index of 27 to 40, and the flame retardant performance may be V0 grade.

Based on this, the present invention further synthesizes flame-retardant silicon-based thermoplastic vulcanizates with the characteristics of permanent flame retardancy, permanent slip and permanent pseudo-abrasion resistance based on the flame-retardant thermoplastic polyurethane synthetic raw materials. In addition to the advantages of general silicon-based thermoplastic vulcanizates, flame-retardant silicon-based thermoplastic vulcanizates also improve UV resistance, thermal stability, weather resistance, and at the same time increase environmentally friendly halogen-free flame retardant characteristics, suitable for hand feel Direct contact products with high requirements, wear resistance, UV resistance and flame retardancy can also be applied to industrial products such as rubber grips, industrial waterproof seals and tool grips for portable measuring instruments.

100‧‧‧Synthetic method of flame retardant silicon-based thermoplastic vulcanizate

110, 120, 130‧‧‧ steps

In order to make the above and other objects, features, advantages and embodiments of the present invention more obvious and understandable, the drawings are described as follows:

FIG. 1 is a flow chart of a method for synthesizing a flame-retardant silicon-based thermoplastic vulcanizate according to an embodiment of the invention.

The embodiments of the present invention will be discussed in more detail below. However, this embodiment can be an application of various inventive concepts and can be specifically implemented in various specific ranges. The specific embodiments are for illustrative purposes only, and are not limited to the scope of disclosure.

Please refer to FIG. 1. FIG. 1 is a flowchart of a method for synthesizing a flame-retardant silicon-based thermoplastic vulcanizate 100 according to an embodiment of the present invention. In FIG. 1, a method 100 for synthesizing a flame-retardant silicon-based thermoplastic vulcanizate includes steps 110, 120, and 130.

Step 110 is to provide a flame-retardant thermoplastic polyurethane synthetic raw material, the flame-retardant thermoplastic polyurethane synthetic raw material comprising a polyisocyanate compound, a macromolecular polyol compound and a small molecule polyol. Specifically, the polyisocyanate may be one kind of isocyanate, or may be a mixture of two or more kinds of isocyanates in any ratio. The average functionality of the isocyanate is greater than or equal to 2, for example, the isocyanate may be an isocyanate containing two isocyanate groups, an isocyanate containing three isocyanate groups, an isocyanate containing more isocyanate groups, or a combination thereof.

The polyisocyanate compound may be, but not limited to, aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, or a combination thereof. For example, the polyisocyanate compound may be, but not limited to, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), methyl 2,6-diisocyanate caproate (LDI), toluene diisocyanate (TDI) , 4,4'-diphenylmethane diisocyanate (MDI) and its modified products, polymethylene polyphenyl isocyanate (PAPI), naphthalene-1,5-diisocyanate (NDI), m-xylylene diisocyanate Isocyanate (XDI), 4,4'-methylene-dicyclohexyl diisocyanate (H12MDI) or 1,12-dodecyl diisocyanate (C12DD10). According to an embodiment of the present invention, the polyisocyanate compound may be selected from 4,4'-diphenyl methane diisocynate (MDI).

As the macromolecular polyol, a polyether polyol or a polyester polyol having a molecular weight of 200 to 3000 and a weight average functionality of 2 to 4 is used. Wherein the polyether polyol may be, but not limited to, polyethylene oxide glycol, polypropylene oxide glycol, polytetrahydrofuran ether glycol or homo- or copolymer diol or polyol of the above monomers; polyester polyol may It is a kind of polyester polyol, or it can be a mixture of two or more kinds of polyester polyols in any proportion. The polyester polyol can be, but not limited to, polyethylene adipate glycol, polyadipate- 1,4-butanediol diol, polyhexamethylene adipate diol, polycaprolactone diol or polycarbonate polyol. According to one embodiment of the present invention, the macromolecular polyol compound may be selected from polypropylene glycol (PPG) with a molecular weight of 700 or 1000, and polytetramethylene ether glycol (PTMEG). And based on the polyisocyanate compound being 100 parts by weight, the content of the macromolecular polyol compound may be 5 parts by weight to 100 parts by weight.

Small molecule polyols can include extender diols and flame-retardant polyols, in which extender diols are chain extenders and are lower aliphatic or short-chain diols containing about 2 to 10 carbon atoms, which can make molecular chains Expansion, and can affect the performance of polyurethane. The extender glycol may be, but not limited to, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,3-butanediol, 1,5 -Pentanediol, 1,4-cyclohexanedimethanol, hydroquinone di(hydroxyethyl) ether or neopentyl glycol, according to one embodiment of the present invention, the extender diol can be selected from 1,4-butane Diol (1,4-butane diol, BOD).

其中，R為氫原子、氫氧基或碳數1至9的烷基，R,,為式(2)或式(3)所示之一結構：

其中，R_x為碳數1至4的烷基或苯基。根據本發明之一實施例，阻燃多元醇可為DOPO系列的二元醇，且具有如式(4)、式(5)或式(6)所示之一結構：

其中式(4)為o-Cresol formaldehyde novolac(CNE,EEW-192)，式(5)為o-Cresol formaldehyde novolac(CNE,EEW-195)，式(6)為o-Cresol formaldehyde novolac(CNE,EEW-200)。且基於多異氰 酸酯化合物為100重量份，小分子多元醇的含量可為5重量份至100重量份。 The flame-retardant polyol is flame-retardant, so that the reactant formed by the flame-retardant polyol and isocyanate is also flame-retardant, which has a structure as shown in formula (1):

Wherein, R is a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 9 carbon atoms, and R, is one of the structures shown in formula (2) or formula (3):

Here, R _x is an alkyl group having 1 to 4 carbon atoms or a phenyl group. According to an embodiment of the present invention, the flame-retardant polyol may be a diol of the DOPO series, and has one of the structures shown in formula (4), formula (5) or formula (6):

Where formula (4) is o-Cresol formaldehyde novolac (CNE, EEW-192), formula (5) is o-Cresol formaldehyde novolac (CNE, EEW-195), and formula (6) is o-Cresol formaldehyde novolac (CNE, EEW-200). And based on the polyisocyanate compound being 100 parts by weight, the content of the small molecule polyol may be 5 parts by weight to 100 parts by weight.

The aforementioned DOPO is a new type of flame retardant. Its structure contains PH bonds, which is very active for olefins, epoxy bonds and carbonyl groups, and can react to form many derivatives. DOPO and its derivatives have a biphenyl ring and The phenanthrene ring structure, especially the pendant phosphorus group is introduced in the form of a cyclic O=PO bond, and has the characteristics of high chemical stability and good flame retardancy. DOPO and its derivatives can be used as reactive and additive flame retardants. They have the advantages of non-toxic, halogen-free, non-migration and long-lasting flame retardant properties. They can be used in a variety of polymer materials such as polyamide, epoxy resin and polyurethane. Make it flame retardant.

The aforementioned flame-retardant thermoplastic polyurethane synthesis raw material is used to synthesize a flame-retardant thermoplastic polyurethane polymer, and the flame-retardant thermoplastic polyurethane polymer may be polyester polyurethane, polyether polyurethane, polycarbonate polyurethane or a blend thereof.

In this way, the above-mentioned polyether polyol or polyester polyol undergoes a polycondensation reaction with the polyisocyanate reactive monomer, and the flame retardant polyol containing a phosphorus group is directly introduced into the main chain or side chain of the unsaturated polyester molecular chain, Compared with the added flame retardant products, the phenomenon of flame retardant migration will not occur, and the mechanical properties, flame retardant properties, electrical properties, etc. of the products can be stable for a long time. Therefore, based on the above flame-retardant thermoplastic polyurethane synthetic raw materials, the present invention further synthesizes a flame-retardant silicon-based thermoplastic vulcanizate.

Step 120 is a prepolymer synthesis step. A silicone rubber base compound is added to the aforementioned flame-retardant thermoplastic polyurethane synthesis raw material and mixed under a high-speed shearing device to obtain a silicone-based thermoplastic vulcanizate prepolymer . The silicone rubber base compound mentioned therein may be diorganopolysiloxane (Diorganopolysiloxane) fluid or resin. Preferably, the silicone rubber base compound may be Polydimethylsiloxane-A (PDMS-A). And based on the polyisocyanate compound being 100 parts by weight, the content of the silicone rubber base compound may be 2 to 50 parts by weight.

Step 130 is to perform a dynamic vulcanization step, put the aforementioned silicone-based thermoplastic vulcanizate prepolymer into a twin-screw extruder, and add a silicone rubber hardener compound to make the silicone-based thermoplastic vulcanizate prepolymer and silicone rubber After the hardener compound is melt blended, it undergoes dynamic vulcanization to achieve a condensation reaction to synthesize a flame-retardant silicon-based thermoplastic vulcanizate. The silicone rubber hardener compound may contain an organic hydrogenated silicon cross-linking agent. Preferably, the silicone rubber hardener compound may be Polydimethylsiloxane-B (PDMS-B). And based on the polyisocyanate compound being 100 parts by weight, the content of the silicone rubber hardener compound may be 2 to 50 parts by weight.

In addition, the above-mentioned dynamic vulcanization step further includes adding a filler and a catalyst, the filler may be diorganopolysiloxane or silicone resin, and the filler further includes a reinforcing filler of diorganopolysiloxane, wherein the two organic The reinforcing filler of polysiloxane may be, but not limited to, silicon dioxide or titanium dioxide. According to an embodiment of the present invention, the filler may be selected from silica to enhance the flame-retardant silicon-based thermoplastic vulcanizate. The catalyst is used to catalyze the condensation reaction, so that the reaction can proceed. Based on the total weight of the polyisocyanate compound is 100 parts by weight, the content of the catalyst can be 0.01 parts by weight to 2 parts by weight, and the catalyst contains one or two inorganic tin Type, platinum substance catalyst or other gold It is a similar system of carboxylate, amine or quaternary ammonium compound, etc. According to one embodiment of the present invention, the catalyst may be selected from bismuth/platinum catalyst.

In this way, the synthesis method 100 of the flame-retardant silicone-based thermoplastic vulcanizate of the present invention saves at least 30% of resources and energy consumption compared with the traditional multi-stage silicone-based thermoplastic vulcanizate process, and at the same time allows nano-grade silicone rubber to Fully and evenly dispersed in the flame retardant thermoplastic polyurethane polymer phase, therefore, the synthesized flame-retardant silicon-based thermoplastic vulcanizate has better mechanical properties, weather resistance and false wear resistance than traditional silicon-based thermoplastic vulcanizate Etc.

The present invention further provides a flame-retardant silicon-based thermoplastic vulcanizate synthesized by the aforementioned synthesis method, which has a Limiting Oxygen Index (LOI) measured from ASTM D-2863 of 27 to 40, preferably In fact, the flame-retardant silicon-based thermoplastic vulcanizate of the present invention can have an oxygen limiting index of 35. Generally, the material with an oxygen-limited index below 22 is a flammable material, a flame-retardant material between 22 and 27, and a highly flame-retardant material above 27, while the conventional oxygen-limited index of thermoplastic polyurethane is only 16 to 18. It is a flammable material.

The flame-retardant silicon-based thermoplastic vulcanizate of the present invention has a flame retardant performance according to the UL94 vertical burning test, and the measurement conditions are 1.90mm in thickness, and the flame retardant grade can best reach V0 grade. The thickness of the plastic burning situation is classified, from the lowest to the highest can be divided into HB, V2, V1 and V0 levels. In addition, the weather resistance performance (48hr, UVA) has also been tested, which can reach more than 4 levels, the low temperature resistance performance can reach -30 ℃, and can withstand fold 100,000 to 200,000 times.

The traditional flame-retardant thermoplastic polyurethane is made by adding flame retardants afterwards. It requires a large amount of flame retardants to reach the V0 level. If it is made into a silicon-based thermoplastic vulcanizate, its mechanical properties will deteriorate. Therefore, the flame-retardant silicon-based thermoplastic vulcanizate of the present invention has the advantages of not only adding a flame retardant, but the composition of the flame-retardant silicon-based thermoplastic vulcanizate synthesized is more uniform, and the physical properties will be close to the original thermoplastic Mechanical properties of polyurethane.

<Example>

The flame-retardant silicon-based thermoplastic vulcanizate of the present invention is synthesized by steps 110 to 130 of the flame-retardant silicon-based thermoplastic vulcanizate synthesis method 100 shown in FIG. Based on synthetic raw materials, the silicone rubber base compound is added to obtain a silicone-based thermoplastic vulcanizate prepolymer under high temperature mixing, then the silicone-based thermoplastic vulcanizate prepolymer is placed in a twin-screw extruder, and the silicone rubber hardener is added The compound undergoes dynamic vulcanization to achieve a condensation reaction to synthesize a flame-retardant silicon-based thermoplastic vulcanizate.

The flame-retardant thermoplastic polyurethane synthesis raw material of Example 1 of the present invention is selected from 4,4'-diphenylmethane diisocyanate (MDI), polypropylene glycol (PPG), polytetrahydrofuran ether glycol (PTMEG) and 1,4-butanedi Alcohol (BDO). Initially synthesized using a one-step method, first 150g polypropylene glycol, 750g polytetrahydrofuran ether glycol and 36g 1,4-butanediol were simultaneously added to the high-speed shear stirring device, stirred at 90 ℃ for 30 minutes, and then added 400g of 4,4'-diphenylmethane diisocyanate, raise the temperature to 180°C and stir for 5 minutes, then add 198g of o-Cresol formaldehyde Novolac (CNE, EEW-192) and 250g of dimethyl siloxane monomer-A (PDMS-A), continue to stir for 3 minutes to synthesize the silicon-based thermoplastic containing dimethyl siloxane monomer-A Vulcanized rubber prepolymer.

Next, put the above-mentioned silicon-based thermoplastic vulcanizate prepolymer into a twin-screw extruder, and add dimethylsiloxane monomer-B (PDMS-B) at a high speed in an environment of 150℃ to 200℃ Mixing, and adding 300ppm of bismuth/platinum catalyst for dynamic vulcanization to achieve the condensation reaction, and finally synthesize a flame-retardant silicon-based thermoplastic vulcanizate.

The flame retardant silicon-based thermoplastic vulcanizate, thermoplastic polyurethane, and conventional silicon-based thermoplastic vulcanizate of Example 1 of the present invention are compared with each other at the same hardness. The results are shown in Table 1 below, where Comparative Example 1 It is a thermoplastic polyurethane, and Comparative Example 2 is a conventional silicone-based thermoplastic vulcanizate.

The flame-retardant thermoplastic polyurethane synthesis raw material of Example 2 of the present invention is selected from 4,4'-diphenylmethane diisocyanate (MDI), polytetrahydrofuran ether glycol (PTMEG) and 1,4-butanediol (BDO). Initially, a one-step method was used for synthesis. First, 600 g of polytetrahydrofuran ether glycol and 36 g of 1,4-butanediol were simultaneously added to the high-speed shear stirring device, and the mixture was stirred at 90° C. for 30 minutes. Then add 400g of 4,4'-diphenylmethane diisocyanate, raise the temperature to 180°C and stir for 5 minutes, then add 292g of o-Cresol formaldehyde novolac (CNE, EEW-195) and 200g of dimethyl silicone Alkyl monomer-A (PDMS-A), stirring continuously for 4 minutes to synthesize a silicone-based thermoplastic vulcanizate prepolymer containing dimethylsiloxane monomer-A.

Next, put the above-mentioned silicon-based thermoplastic vulcanizate prepolymer into a twin-screw extruder, and add dimethylsiloxane monomer-B (PDMS-B) at a high speed in an environment of 150℃ to 200℃ Mixing, and additionally adding 152g of silicon dioxide and 350ppm of bismuth/platinum catalyst, dynamic vulcanization to achieve the condensation reaction, and finally synthesized a flame-retardant silicon-based thermoplastic vulcanizate.

The flame retardant silicon-based thermoplastic vulcanizate, thermoplastic polyurethane, and conventional silicon-based thermoplastic vulcanizate of Example 2 of the present invention are compared with each other at the same hardness. The results are shown in Table 2 below, where Comparative Example 3 It is a thermoplastic polyurethane, and Comparative Example 4 is a conventional silicone-based thermoplastic vulcanizate.

It can be seen from the results in Tables 1 and 2 above that at the same hardness, the flame-retardant silicon-based thermoplastic vulcanizate of the present invention is comparable to the conventional thermoplastic Polyurethane and silicon-based thermoplastic vulcanizates have excellent flame retardancy, abrasion resistance and weather resistance, and the silica-reinforced filler added in Example 2 enhances the mechanical properties and hardness of Example 2.

In summary, the flame-retardant silicon-based thermoplastic vulcanizate synthesized by the synthesis method of the flame-retardant silicon-based thermoplastic vulcanizate of the present invention has excellent flexibility, permanent flame retardant behavior, and permanent weather resistance Flame retardant, non-halogen flame retardant, can delay the speed of fire spread, and can also reduce the poisonous gas damage during combustion, and the production cost of the invention Low waste and less waste, with greater implementation value and social and economic benefits.

Although the present invention has been disclosed as above in an embodiment, it is not intended to limit the present invention. Anyone who is familiar with this art can make various modifications and retouching without departing from the spirit and scope of the present invention, so the protection of the present invention The scope shall be as defined in the appended patent application scope.

100‧‧‧Synthetic method of flame retardant silicon-based thermoplastic vulcanizate

110, 120, 130‧‧‧ steps

Claims (16)

A method for synthesizing a flame-retardant silicon-based thermoplastic vulcanizate, comprising: providing a flame-retardant thermoplastic polyurethane synthetic raw material, the flame-retardant thermoplastic polyurethane synthetic raw material comprising a polyisocyanate compound, a macromolecular polyol compound and a small molecule polyol, wherein The molecular weight of the macromolecular polyol compound is 200 to 3000, the small molecule polyol contains an extender diol and a flame retardant polyol, and the extender diol contains 2 to 10 carbon atoms; a prepolymer synthesis step is performed , A silicone rubber base compound is added to the flame-retardant thermoplastic polyurethane synthetic raw material, and mixed under a high-speed shearing device to obtain a silicone-based thermoplastic vulcanizate prepolymer; and a dynamic vulcanization step is performed to The silicone-based thermoplastic vulcanizate prepolymer is put into a twin-screw extruder and a silicone rubber hardener compound is added to melt and blend the silicone-based thermoplastic vulcanizate prepolymer and the silicone rubber hardener compound before proceeding. It is dynamically vulcanized to achieve a condensation reaction to synthesize the flame-retardant silicon-based thermoplastic vulcanizate. The method for synthesizing a flame-retardant silicon-based thermoplastic vulcanizate as described in item 1 of the patent application scope, wherein the flame-retardant thermoplastic polyurethane synthesis raw material is used to synthesize a flame-retardant thermoplastic polyurethane polymer, and the flame-retardant thermoplastic polyurethane The polymer is polyester polyurethane, polyether polyurethane, polycarbonate polyurethane or a blend thereof. The method for synthesizing a flame-retardant silicon-based thermoplastic vulcanizate as described in item 1 of the patent application scope, wherein the total weight of the polyisocyanate compound is 100 parts by weight and the content of the macromolecular polyol compound is 5 parts by weight To 100 parts by weight, the content of the small molecule polyol is 5 to 100 parts by weight. The method for synthesizing a flame-retardant silicon-based thermoplastic vulcanizate as described in item 1 of the patent application scope, wherein the flame-retardant polyol is a DOPO series glycol and has formulas (4) and (5) Or one of the structures shown in formula (6):

The method for synthesizing a flame-retardant silicone-based thermoplastic vulcanizate as described in item 1 of the patent application scope, wherein the silicone rubber base compound is a diorganopolysiloxane fluid or resin. The method for synthesizing a flame-retardant silicone-based thermoplastic vulcanizate as described in item 5 of the patent application scope, wherein the silicone rubber base compound is dimethyl siloxane monomer. The method for synthesizing a flame-retardant silicon-based thermoplastic vulcanizate as described in item 1 of the patent application scope, wherein the silicone rubber hardener compound contains an organic hydrogenated silicon crosslinking agent. The method for synthesizing a flame-retardant silicon-based thermoplastic vulcanizate as described in item 7 of the patent application scope, wherein the silicone rubber hardener compound is dimethyl siloxane monomer. The method for synthesizing a flame-retardant silicon-based thermoplastic vulcanizate as described in item 1 of the patent application scope, wherein the total weight of the polyisocyanate compound is 100 parts by weight, and the content of the silicone rubber base compound is 2 parts by weight To 50 parts by weight, the content of the silicone rubber hardener compound is 2 to 50 parts by weight. The method for synthesizing a flame-retardant silicon-based thermoplastic vulcanizate as described in item 1 of the patent application scope, wherein the dynamic vulcanization step further includes adding a filler, and the filler is diorganopolysiloxane or silicone resin. The method for synthesizing a flame-retardant silicon-based thermoplastic vulcanizate as described in item 10 of the patent application scope, wherein the filler further includes a reinforced filler of diorganopolysiloxane. The method for synthesizing a flame-retardant silicon-based thermoplastic vulcanizate as described in item 1 of the patent application scope, wherein the dynamic vulcanization step further includes adding a catalyst, and the catalyst is used to catalyze the condensation reaction. The method for synthesizing a flame-retardant silicon-based thermoplastic vulcanizate as described in item 12 of the patent application scope, wherein the total weight of the polyisocyanate compound is 100 parts by weight and the content of the catalyst is 0.01 to 2 parts by weight . A flame-retardant silicon-based thermoplastic vulcanizate is synthesized by the synthesis method of the flame-retardant silicon-based thermoplastic vulcanizate as described in any one of the patent application items 1 to 13. The flame-retardant silicon-based thermoplastic vulcanizate as described in item 14 of the patent application scope, wherein the flame-retardant silicon-based thermoplastic vulcanizate has an oxygen limiting index of 27 to 40. The flame-retardant silicon-based thermoplastic vulcanizate as described in item 14 of the patent application scope, wherein the flame-retardant silicon-based thermoplastic vulcanizate has a flame retardant performance of V0 grade.

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