CN100482739C - Flame retardant, antistatic unsaturated polyester resin - Google Patents

Flame retardant, antistatic unsaturated polyester resin Download PDF

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Publication number
CN100482739C
CN100482739C CNB2006100201788A CN200610020178A CN100482739C CN 100482739 C CN100482739 C CN 100482739C CN B2006100201788 A CNB2006100201788 A CN B2006100201788A CN 200610020178 A CN200610020178 A CN 200610020178A CN 100482739 C CN100482739 C CN 100482739C
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Prior art keywords
unsaturated polyester
parts
polyester resin
antistatic
retardant
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CNB2006100201788A
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CN1803918A (en
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杨锋
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SICHUAN JIUDA NEW COMPOSITE MATERIAL CO Ltd
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SICHUAN JIUDA NEW COMPOSITE MATERIAL CO Ltd
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Abstract

The invention discloses a flame-proof and electrostatic resistant unsaturated polyester resin for manufacturing glass reinforced plastic gas pipes of coal mines, which comprises the following ingredients (by weight portions): unsaturated polyester resin 100 parts, decabromodiphenyl oxide 22-26 parts, antimony trioxide 3-6 parts, and acetylene carbon black 1.5-3 parts.

Description

A kind of fire-retardant, antistatic unsaturated polyester resin
Technical field
The invention belongs to the macromolecule chemical industry field, especially relate to a kind of fire-retardant, antistatic unsaturated polyester resin that additive preparation becomes that add, be applicable to and make underground mine use glass reinforced plastic gas pipe.
Background technology
Fire-retardant, antistatic unsaturated polyester resin is a main raw material(s) of making underground mine use glass reinforced plastic gas pipe, and fire-retardant, the antistatic property of glass reinforced plastic gas pipe all fire-retardant, the antistatic unsaturated polyester resin after solidify obtains.At present, the producer of domestic production glass reinforced plastic gas pipe is a lot, but the glass reinforced plastic gas pipe of producing all has the shortcoming of poor mechanical property mostly, the gas pipe poor mechanical property is because make the fire-retardant of gas pipe, the mechanical properties decrease of antistatic unsaturated polyester resin causes, because unsaturated polyester resin itself does not have fire-retardant, anlistatig performance, so, generally all adopt and add fire retardant, it is fire-retardant that the method for static inhibitor obtains unsaturated polyester resin, antistatic property, but the mechanical property of its unsaturated polyester resin goods has descended greatly when additive adds.The reason of mechanical properties decrease mainly is: 1, in order to satisfy the requirement of coal-mining industry ministerial standard " underground mine use plastics tubing safety performance inspection specification " (MT 181-88) regulation, the addition of fire retardant, static inhibitor is bigger, has influenced the mechanical and physical performance of glass fiber reinforced plastics product; 2, some fire retardants, static inhibitor have certain inhibition, make the degree of cure of unsaturated polyester resin be difficult to reach requirement, have influenced the mechanical property of glass fiber reinforced plastics product.The decline of goods mechanical property, cause the underground mine use fiber reinforced plastic pipe in use to cause accident to take place easily, as because glass reinforced plastic gas releasing pipe bears the negative pressure ability drop and destroys structural pipe wall easily, cause serious consequences such as pipeline breaking, damage, influenced the effect of gas drainage.
Summary of the invention
The purpose of this invention is to provide a kind of fire-retardant, antistatic unsaturated polyester resin prescription, when unsaturated polyester resin obtains fire-retardant, antistatic property, make its goods have higher mechanical property.
The object of the present invention is achieved like this:
A kind of fire-retardant, antistatic unsaturated polyester resin, formed by following compositions in weight portion:
100 parts of unsaturated polyester resins
Decabromodiphenyl oxide 22-26 part
Antimonous oxide 3-6 part
Shawinigan black 1.5-3 part
Prescription is preferably:
100 parts of unsaturated polyester resins
Decabromodiphenyl oxide 23-26 part
Antimonous oxide 4-5 part
Shawinigan black 1.5-3 part
Best prescription is:
100 parts of unsaturated polyester resins
25 parts of decabromodiphenyl oxides
5 parts of antimonous oxides
3 parts of Shawinigan blacks.
Production method of the present invention is very simple, is about to each component and takes by weighing by described weight ratio, adds decabromodiphenyl oxide, antimonous oxide, Shawinigan black successively in unsaturated polyester resin, and stirring by stirrer gets final product.
After this prescription process our company test of many times, on the basis of great number tested data, finally determined optimum formula.This prescription has following characteristics:
The one, decabromodiphenyl oxide is a kind of addition type efficient flame-retarding agent, the high brominated amount of tool, Heat stability is good, the characteristics that addition is little.The decabromodiphenyl oxide physicochemical characteristic is as follows:
Molecular weight: 959.2 outward appearances: white powder
Melt temperature: 300-310 ℃ bromine content: 83.3%
Proportion: 3.2 mean particle sizes: 3.2 μ m
Free bromine content:<20PPM
Thermal weight loss characteristic: 5%@320 ℃; 10%@334 ℃; 50%@373 ℃; 95%@361 ℃
The 2nd, antimonous oxide is a kind of fire retardant commonly used, is used with decabromodiphenyl oxide to have fabulous fire-retardant synergy.
Sb 2O: 99.8% mean particle size: 0.36 μ m
The 3rd, Shawinigan black has big surface-area, and conductivity is good, and addition is little.
The 4th, above each component adds can make resin obtain best flame retardant properties and conductivity in the unsaturated polyester resin, and less to the mechanical property influence of resin.Addition is excessive, and then remarkable decline of the mechanical property of resin and material cost will rise.Addition is too small, and then the flame retardant properties of resin and conductivity can not effectively be guaranteed.For this reason, do following experiment and obtained optimum formula:
Experiment 1 (by less fire retardant, static inhibitor addition)
Prescription 1: 100 parts of unsaturated polyester resins, 20 parts of decabromodiphenyl oxides, 3 parts of antimonous oxides, 1 part of Shawinigan black.
Its flame retardant properties of fire-retardant, antistatic fiber reinforced plastic pipe (is example with DN200 gas pipe 0.6MPa), antistatic property, the mechanical property of making by above-mentioned prescription see Table 1:
Figure C200610020178D00061
Experiment 2 (optimum formulas)
Prescription 2: 100 parts of unsaturated polyester resins, 25 parts of decabromodiphenyl oxides, 5 parts of antimonous oxides, 3 parts of Shawinigan blacks
Its flame retardant properties of fire-retardant, antistatic fiber reinforced plastic pipe (is example with DN200 gas pipe 0.6MPa), antistatic property, the mechanical property of making by above-mentioned prescription see Table 2:
Experiment 3 (fire retardant is by bigger addition)
Prescription 3: 100 parts of unsaturated polyester resins, 30 parts of decabromodiphenyl oxides, 6 parts of antimonous oxides, 3 parts of Shawinigan blacks.
Its flame retardant properties of fire-retardant, antistatic fiber reinforced plastic pipe (is example with DN200 gas pipe 0.6Mpa), antistatic property, the mechanical property of making by above-mentioned prescription see Table 3:
Figure C200610020178D00081
As can be seen from the above results, press fire-retardant, the antistatic unsaturated polyester resin of the formulated of experiment 1, the flame retardant properties of its goods, surface conduction performance all can not satisfy the requirement of standard; Press fire-retardant, the antistatic unsaturated polyester resin of the formulated of experiment 3, the mechanical properties decrease of its goods is very fast, can not satisfy the requirement of standard; By fire-retardant, the antistatic unsaturated polyester resin of experiment 2 optimum formulas preparation, the flame retardant properties of its goods, surface conduction performance, mechanical property can satisfy the requirement of standard fully.
Adopt the present invention to make glass reinforced plastic gas releasing pipe by Wrapping formed method, according to the building materials ministerial standard: " (fiber twines and strengthens the thermosetting resin penstock " (JC552-94) and the coal-mining industry ministerial standard: " underground mine use plastics tubing safety performance inspection specification " (MT 181-88) specified requirement detects, and this glass reinforced plastic gas releasing pipe has following characteristic:
Glass reinforced plastic gas discharge in mine pipe main performance index with the present invention's making:
Figure C200610020178D00091
Use fire-retardant, the antistatic property and the mechanical property of glass reinforced plastic gas releasing pipe (annotate: 0.6Mpa is example with the DN200 gas pipe) that the present invention makes to see the following form:
Figure C200610020178D00101
Advantage of the present invention is: 1. adopt high-quality fire retardant, static inhibitor, and fire-retardant, the antistatic unsaturated polyester resin of preparation, its goods have higher mechanical property; 2. stable performance, the glass reinforced plastic gas pipe that adopts this prescription to make meets the security regulations and the requirement of country, industry relevant criterion fully: 3. preparation method's simple and fast, storage period is permanent.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail, but the present invention has more than and is limited to these examples:
Embodiment 1: a kind of fire-retardant, antistatic unsaturated polyester resin, formed by following compositions in weight portion:
100 parts of unsaturated polyester resins
22 parts of decabromodiphenyl oxides
6 parts of antimonous oxides
3 parts of Shawinigan blacks
Making method: 1. by spiral pump with in the unsaturated polyester resin suction stirred pot; 2. start stirrer; 3. start flat vibrating screen, pour the fire retardant decabromodiphenyl oxide into to hopper in batches, progressively open the dish valve then, make the decabromodiphenyl oxide powder evenly enter vibrating screen surface, thereby evenly enter the resin liquid level, by resin liquid pressed powder is brought into to shear in the liquid and force to stir, reach homogeneous immersion; 4. start flat vibrating screen, pour the antimonous oxide of the capacity of processing requirement into, progressively open the dish valve then to hopper, make powder evenly enter vibrating screen surface, thereby evenly enter the resin liquid level, by resin liquid pressed powder is brought into to shear in the liquid and force to stir, reach homogeneous immersion; 5. start flat vibrating screen, pour the static inhibitor Shawinigan black into to hopper in batches, progressively open the dish valve then, make powder evenly enter vibrating screen surface, thereby evenly enter the resin liquid level, by resin liquid pressed powder is brought into to shear in the liquid and force to stir, reach homogeneous immersion; 6. after material all adds resin by the processing requirement capacity, continue to stir 60 minutes, in resin, stir until material; 7. stop stirrer, the resin for preparing is left standstill start stirrer once more after 30 minutes, stir and got final product in 20 minutes.
The prepared unsaturated polyester of the present invention possesses following characteristic
Figure C200610020178D00121
Embodiment 2: a kind of fire-retardant, antistatic unsaturated polyester resin, formed by following compositions in weight portion:
100 parts of unsaturated polyester resins, 26 parts of decabromodiphenyl oxides, 3 parts of antimonous oxides, 1.5 parts of Shawinigan blacks.
Prepare fire-retardant, antistatic unsaturated polyester resin by method among the embodiment 1, this resin possesses following characteristic:
Embodiment 3: a kind of fire-retardant, antistatic unsaturated polyester resin, formed by following compositions in weight portion:
100 parts of unsaturated polyester resins, 23 parts of decabromodiphenyl oxides, 5 parts of antimonous oxides, 2 parts of Shawinigan blacks.
Prepare fire-retardant, antistatic unsaturated polyester resin by method among the embodiment 1, this resin possesses following characteristic:
Embodiment 4: a kind of fire-retardant, antistatic unsaturated polyester resin, formed by following compositions in weight portion:
100 parts of unsaturated polyester resins
24 parts of decabromodiphenyl oxides
4 parts of antimonous oxides
3 parts of Shawinigan blacks
Prepare fire-retardant, antistatic unsaturated polyester resin by method among the embodiment 1, this resin possesses following characteristic:
Figure C200610020178D00151
Embodiment 5: a kind of fire-retardant, antistatic unsaturated polyester resin, formed by following compositions in weight portion:
100 parts of unsaturated polyester resins
25 parts of decabromodiphenyl oxides
5 parts of antimonous oxides
3 parts of Shawinigan blacks
Prepare by method among the embodiment 1 fire-retardant, antistatic unsaturated polyester resin, this resin possesses following characteristic:
The unsaturated polyester resin that above-mentioned any prescription is made, can both satisfy the building materials ministerial standard: " fiber twine strengthen thermosetting resin penstock " (JC552-94) and the coal-mining industry ministerial standard: the requirement of " underground mine use plastics tubing safety performance inspection specification " (MT 181-88) is applicable to the fiber reinforced plastic pipe of making the colliery special use.

Claims (3)

1, a kind of fire-retardant, antistatic unsaturated polyester resin is characterized in that being made up of following compositions in weight portion:
100 parts of unsaturated polyester resins
Decabromodiphenyl oxide 22-26 part
Antimonous oxide 3-6 part
Shawinigan black 1.5-3 part.
2, fire-retardant, antistatic unsaturated polyester resin according to claim 1 is characterized in that being made up of following compositions in weight portion:
100 parts of unsaturated polyester resins
Decabromodiphenyl oxide 23-26 part
Antimonous oxide 4-5 part
Shawinigan black 1.5-3 part.
3, unsaturated polyester resin according to claim 2 is characterized in that being made up of following compositions in weight portion:
100 parts of unsaturated polyester resins
25 parts of decabromodiphenyl oxides
5 parts of antimonous oxides
3 parts of Shawinigan blacks.
CNB2006100201788A 2006-01-17 2006-01-17 Flame retardant, antistatic unsaturated polyester resin Expired - Fee Related CN100482739C (en)

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Application Number Priority Date Filing Date Title
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CN100482739C true CN100482739C (en) 2009-04-29

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101948656B (en) * 2010-10-13 2012-08-22 广东华江粉末科技有限公司 Ceiling powder paint and preparation method thereof
CN110054879A (en) * 2019-04-02 2019-07-26 苏州海晨塑胶有限公司 A kind of flame-retardant and anti-static polyester material and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN88101600A (en) * 1988-03-24 1988-11-16 广州市消防科学技术研究所 Flame retardant unsaturated polyester resin composite and goods thereof
CN1076708A (en) * 1992-03-20 1993-09-29 傅宏生 Flame-retarding anti-static coating and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN88101600A (en) * 1988-03-24 1988-11-16 广州市消防科学技术研究所 Flame retardant unsaturated polyester resin composite and goods thereof
CN1076708A (en) * 1992-03-20 1993-09-29 傅宏生 Flame-retarding anti-static coating and preparation method thereof

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