CN110734551A - high-strength high-heat-resistant flame-retardant transparent polycarbonate resin and preparation method thereof - Google Patents
high-strength high-heat-resistant flame-retardant transparent polycarbonate resin and preparation method thereof Download PDFInfo
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- CN110734551A CN110734551A CN201910908417.0A CN201910908417A CN110734551A CN 110734551 A CN110734551 A CN 110734551A CN 201910908417 A CN201910908417 A CN 201910908417A CN 110734551 A CN110734551 A CN 110734551A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/395—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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Abstract
The invention provides transparent polycarbonates with high strength and high heat resistance and flame retardance and a preparation method thereof, wherein polycarbonate resin and a phosphorus-silicon flame retardant are uniformly mixed and then prepared by a melt extrusion process, the phosphorus-silicon flame retardant is prepared by modifying DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) by using allyl alcohol, and the modified structure is reacted with phenyl hydrogen-containing silicone resin.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to high-strength, high-heat-resistant and flame-retardant transparent polycarbonate and a preparation method thereof.
Background
Polycarbonate (PC) is a thermoplastic engineering plastic with good comprehensive performance, and due to the structural particularity, the polycarbonate has the characteristics of excellent light transmission, impact toughness, electrical insulation, weather resistance and the like, is widely applied to the industries of electronics, electric appliances, aerospace, automobiles and the like.
With the increasing development of industries such as electronic and electric appliances, aerospace, automobile components and the like, the requirement on the flame retardance of polycarbonate is more and more strict, the polycarbonate has the flame retardance of , the oxygen index of the polycarbonate can reach about 25, the polycarbonate can pass the UL 94V-2 test, but the polycarbonate needs to be subjected to flame retardant modification treatment to meet the requirement on high flame retardance.
The common flame retardant comprises halogens, phosphorus, silicon, sulfonate and the like, wherein the halogens seriously affect the light transmittance and impact strength of PC, the sulfonate flame retardant has good flame retardant effect and has small influence on the light transmittance of polycarbonate, but the sulfonate contains sulfur and can cause harm to the environment and human bodies.
Disclosure of Invention
The invention aims to synthesize novel flame retardants simultaneously containing phosphorus and silicon elements aiming at the defects of the prior art, and add the flame retardants into polycarbonate resin to prepare transparent polycarbonate resins with high strength, high heat resistance and flame retardance.
The invention firstly provides a preparation method of a flame retardant containing phosphorus and silicon elements, which comprises the following steps:
(1) quantitative DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) and an organic solvent are taken and added into a three-necked bottle provided with a condensing reflux device, and CCl is slowly dripped under the ice bath condition4After the dripping is finished, continuously adding the propylene alcohol and the triethylamine into the system, reacting for hours, raising the temperature of the system, and carrying out heat preservation reaction And cooling to room temperature after a while, filtering, washing and drying the crude product to obtain the allyl alcohol modified DOPO.
(2) And (2) dissolving the product obtained in the step (1) in cyclohexane, adding phenyl hydrogen-containing silicone resin, uniformly stirring, removing the solvent under reduced pressure, adding Karstedt catalyst, and reacting to obtain the target product.
The process is represented by a chemical reaction formula as follows:
the structure of the flame retardant containing phosphorus and silicon is as follows:
in the step (1), the organic solvent is or a mixture of any proportion of 1,4 dioxane, chloroform, tetrahydrofuran, acetone and dichloromethane, and the proportion of DOPO and the organic solvent can be 1g (1-30 ml).
In the step (1), the molar ratio of DOPO to allyl alcohol is 1 (1-3).
In the step (1), the molar ratio of DOPO to carbon tetrachloride is 1: 1-3.
In the step (1), the molar ratio of DOPO to triethylamine is 1: 1-3.
The ice-bath condition in the step (1): the reaction temperature is less than 15 ℃, and the reaction time is 0.5-2 h.
And (2) heating for reaction in the step (1), wherein the reaction temperature is 20-50 ℃, and the reaction time is 4-10 hours.
In the step (2), the molar ratio of the product of the step (1) to the phenyl hydrogen-containing silicone resin is (1-6): 1.
The phenyl hydrogen-containing silicone resin in the step (2) is a commercially available product, and the trade mark is as follows: the SH-8 structure is as follows:
A preparation method of high-strength, high-heat-resistance and flame-retardant transparent polycarbonate resin, comprising the following steps:
(a) preparing the following materials in percentage by weight: 80-99% of polycarbonate and 1-20% of phosphorus-silicon flame retardant;
(b) drying polycarbonate at 100-140 ℃ for 4-10 h, uniformly mixing the dried polycarbonate resin and the phosphorus-silicon flame retardant, adding the mixture into a double-screw extruder, extruding, drawing, granulating at 220-280 ℃, and drying to obtain the flame-retardant transparent polycarbonate resin material.
The phosphorus-silicon flame retardant in the step (a) is obtained by the preparation method of the flame retardant containing phosphorus and silicon elements.
The invention has the advantages and effects that:
according to the invention, novel phosphorus-silicon-containing flame retardants are synthesized, and due to the structural particularity, the polyphenyl phosphate structure and the polyphenyl spherical siloxane structure contained in the structure are added into polycarbonate resin, so that the flame retardant property and the mechanical strength of the polycarbonate are improved on the basis of not influencing the transmittance of the polycarbonate.
Detailed Description
The present invention will be described in detail with reference to examples.
EXAMPLE 1 Synthesis of phosphorus silicon flame retardant
(1) Adding 4.32g of DOPO and 20ml of dichloromethane into a three-necked bottle provided with a condensing reflux device, and slowly dropwise adding 4ml of CCl under the ice bath condition4After the dropwise addition, continuously adding 1.2g of propylene alcohol and 4ml of triethylamine into the system, reacting for periods, raising the temperature of the system, keeping the temperature for periods, cooling to room temperature, filtering, washing and drying the crude product to obtain the propylene alcohol modified DOPO.
(2) And (2) dissolving 11.5g of the product obtained in the step (1) in cyclohexane, adding 7.52g (0.01mol) of phenyl hydrogen-containing silicone resin, uniformly stirring, removing the solvent under reduced pressure, adding a Karstedt catalyst, and finally reacting to obtain the target product.
Examples 2-6 preparation of high-Strength, high Heat-resistant, flame-retardant transparent polycarbonate resins
Examples 2-6, the weight percentages of the components in each example are shown in table 1.
The specific steps are as follows, drying the PC resin for 4 hours at the temperature of 120 ℃, and uniformly mixing the PC resin and the flame retardant according to the proportion. Adding the mixture into a double-screw extruder for melt blending extrusion; wherein the temperature of each zone of the double-screw extruder is 260 ℃, 265 ℃, 270 ℃, 270 ℃, 265 ℃ and the head temperature is 270 ℃, and the extruded raw materials are subjected to traction, granulation and drying to obtain the transparent flame-retardant PC material. The resulting transparent PC material was injection-molded into 3.0mm thick bars by means of an injection-molding machine and the performance tests were carried out according to the corresponding standards (see Table 2).
The test results are shown in Table 3.
Table 1: formulation compositions of examples 2-6
| Components | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Polycarbonate resin | 98％ | 96％ | 94％ | 92％ | 90％ |
| Phosphorus silicon flame retardant | 2％ | 4％ | 6％ | 8％ | 10％ |
TABLE 2 test standards
| Item | Unit of | Test conditions | Test standard |
| Tensile strength | MPa | 23℃ | ASTM D 638 |
| Elongation at break | ％ | 50mm/min | ASTM D 638 |
| Impact strength | KJ/m3 | 23℃ | ASTM D 256 |
| UL94 | 3.0mm | / | ASTM 2863 |
| Oxygen index | ％ | / | ASTM 2863 |
| Transmittance of light | ％ | 23℃ | ASTM D1003 |
TABLE 3 mechanical Properties and flame retardancy of polycarbonates tested in examples 2-6
| Performance of | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Tensile strength | 61.6 | 63.7 | 65.5 | 70.1 | 68.9 |
| Elongation at break | 120 | 125 | 125 | 120 | 117 |
| Impact strength | 53.8 | 59.6 | 59.9 | 60.5 | 60.7 |
| UL-94(3mm) | V-0 | V-0 | V-0 | V-0 | V-0 |
| Transmittance of light | 87.1 | 86.9 | 86.7 | 86.0 | 85.0 |
TABLE 4 thermal weight loss test data for polycarbonates of examples 2-6
| Test specimen | T-5％(℃) | T-50％(℃) | T-70％(℃) |
| Example 2 | 399.7 | 448.2 | 471.4 |
| Example 3 | 423 2 | 471.9 | 501.2 |
| Example 4 | 425 9 | 482.0 | 503.9 |
| Example 5 | 427 0 | 469.1 | 500.1 |
| Example 6 | 415.1 | 449.0 | 479.9 |
As can be seen from the results of the performance tests in tables 3 and 4, the mechanical strength and the thermal stability of the polycarbonate are improved on the basis of ensuring the light transmittance of the polycarbonate by adding the phosphorus-silicon flame retardant, and the optimal formula can be determined through tests.
While the invention has been described in terms of specific embodiments , these embodiments are merely exemplary and not intended to limit the scope of the invention.
Claims (10)
1, phosphorus-silicon element-containing flame retardant, which has the following structure:
2. the method of claim 1 for preparing phosphorus-silicon containing flame retardants, comprising the steps of:
(1) quantitative DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) and an organic solvent are taken and added into a three-necked bottle provided with a condensing reflux device, and CCl is slowly dripped under the ice bath condition4After the dripping is finished, continuously adding the propylene alcohol and the triethylamine into the system, reacting for hours, raising the temperature of the system, keeping the temperature for hours, cooling to room temperature, filtering, washing and drying the crude product to obtain propylene alcohol modified DOPO;
(2) and (2) dissolving the product obtained in the step (1) in cyclohexane, adding phenyl hydrogen-containing silicone resin, uniformly stirring, removing the solvent under reduced pressure, adding Karstedt catalyst, and reacting to obtain the target product.
3. The method for preparing phosphorus-silicon containing flame retardants of claim 2, wherein the organic solvent in step (1) is or more selected from 1,4 dioxane, chloroform, tetrahydrofuran, acetone, and dichloromethane, and the ratio of DOPO to the organic solvent is 1g (1-30 ml).
4. The preparation method of phosphorus-silicon element-containing flame retardants according to claim 2, wherein the molar ratio of DOPO to allyl alcohol in the step (1) is 1 (1-3).
5. The method for preparing phosphorus-silicon containing flame retardants of claim 2, wherein the molar ratio of DOPO to carbon tetrachloride in step (1) is 1: 1-3.
6. The preparation method of phosphorus-silicon element-containing flame retardants according to claim 2, wherein the molar ratio of DOPO to triethylamine in the step (1) is 1: 1-3.
7. The preparation method of phosphorus-silicon element-containing flame retardants of claim 2, wherein the step (1) comprises an ice bath under conditions of a reaction temperature of less than 15 ℃ and a reaction time of 0.5-2 h, and the reaction temperature of the temperature-raising reaction is 20-50 ℃ and the reaction time is 4-10 h.
8. The method for preparing phosphorus-silicon-element-containing flame retardants according to claim 2, wherein in the step (2), the molar ratio of the product of the step (1) to the phenyl hydrogen-containing silicone resin is (1-6): 1.
9, A preparation method of high-strength, high-heat-resistance and flame-retardant transparent polycarbonate resin, comprising the following steps:
(a) preparing the following materials in percentage by weight: 80-99% of polycarbonate and 1-20% of phosphorus-silicon flame retardant;
(b) drying the polycarbonate resin at 100-140 ℃ for 4-10 h, uniformly mixing the dried polycarbonate resin with a phosphorus-silicon flame retardant, adding the mixture into a double-screw extruder, extruding, drawing and granulating at 220-280 ℃, and drying to obtain a flame-retardant transparent polycarbonate resin material;
the phosphorus-silicon flame retardant in the step (a) is obtained by the preparation method according to claim 2.
10. The phosphorus-silicon element-containing flame retardant preparation method of claim 2, wherein the phenyl hydrosilicon resin in step (2) has the following structure:
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114213710A (en) * | 2021-12-16 | 2022-03-22 | 锦西化工研究院有限公司 | Novel flame retardant and high-temperature flame-retardant transparent polycarbonate resin |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114213710A (en) * | 2021-12-16 | 2022-03-22 | 锦西化工研究院有限公司 | Novel flame retardant and high-temperature flame-retardant transparent polycarbonate resin |
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