CN1209414C - Fire retardant polyester resin composition - Google Patents
Fire retardant polyester resin composition Download PDFInfo
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- CN1209414C CN1209414C CN 02142242 CN02142242A CN1209414C CN 1209414 C CN1209414 C CN 1209414C CN 02142242 CN02142242 CN 02142242 CN 02142242 A CN02142242 A CN 02142242A CN 1209414 C CN1209414 C CN 1209414C
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Abstract
The present invention relates to a combustion-resistant polyester resin composition which contains polyester resin, red phosphorus and melamine-phenolic resin. The combustion-resistant polyester resin composition of the present invention does not contain halogens and antimony trioxide. The combustion-resistant polyester resin composition has the advantages of good combustion resistance and excellent mechanical strength, and can be used for manufacturing parts of formed products in the fields of electronics, electricity, information, communication and automobiles.
Description
Technical field
The present invention relates to a kind of not halogen-containing flame-retardant polyester resin composition with flame-retardant nature and excellent mechanical strength.
Background technology
Vibrin has excellent mechanical properties, thermotolerance and chemical resistant properties, and has advantages such as excellent machining property and recyclable processing, therefore has been widely used in the molded object of electronics, electric, information, communication and automotive industry.
Yet in these were used, the flame-retarding characteristic of vibrin was the prerequisite of these application, thereby industry develops the vibrin raw material with flame retardant resistance.In already known processes, bromated fire retardant of development utilization and antimonous oxide with flame retardant resistance are matched with in the vibrin reaching fire-retardant purpose, but known these fire retardants have hazardness to human body and animal.For example antimonous oxide has been listed in carcinogenic substance, and bromated fire retardant not only can produce acrid bromine radical and hydrogen bromide in the vibrin combustion processes, and the aryl compound of high bromine content more can produce bromination the mutter class and the bromination Dioxins compound of severe toxicity, has a strong impact on HUMAN HEALTH and harm environment.Therefore domestic and international in recent years many products have required not contain the vibrin product of antimony and bromide fire retardant.
Based on these reasons, extensively utilize phosphorus series compound for example triphenyl as fire retardant, yet be applied in the vibrin, especially be applied in the polybutylene terephthalate, because the molecular weight of triphenyl is low, to separate out (bleedout) problem, and finished product outward appearance, electrical properties etc. are penetrated in influence, cause the puzzlement in the practicality.
In addition, USP 5,814,690 disclose a kind of thermoplastic molding compoistions, wherein use melamine pyrophosphate to cooperate aromatics phosphoric acid salt as fire retardant, though this fire retardant can make polybutylene terephthalate obtain good flame retardant effect, it is not enough that its physical strength is still disliked.
In addition, USP 6,133, and 358 disclose a kind of not halogen-containing fire retardant polyester and resin composition, wherein use the red phosphorus powder as fire retardant.But the flame retardant resistance of these compositions still has weak point.
The inventor is based on the shortcoming of above-mentioned already known processes, and is purpose to improve mechanical properties, polyester and resin composition carried out broad research, thereby finish the present invention.
Summary of the invention
The present invention relates to a kind of flame-retardant polyester resin composition, comprise vibrin, red phosphorus and cyanurotriamide modified resol.
More particularly, the present invention relates to a kind of flame-retardant polyester resin composition, comprising: (A) Celanex resin 100 weight parts, (B) cyanurotriamide modified resol 5 to 50 weight parts, and (C) red phosphorus 2 to 20 weight parts.
Flame-retardant composition of the present invention is not halogen-containing, thereby have good mechanical properties and do not have the surface and separate out problem, and the time do not have to hang down in burning by the prepared moulding product of said composition and drip a phenomenon, thereby can be applicable to the molded object of electronics, electric, information, communication and automotive industry.
Used Celanex resin for example can use by aromatic dicarboxylic acid such as phthalic acid or naphthalic acid or its ester as sour composition and C2-6 aliphatic diol or its ester as the polyester of pure composition through the reaction gained in the flame retardant resin composition of the present invention.The particular instance of this Celanex resin comprises for example polyethylene terephthalate, poly-naphthalene diformic acid dimethyl ester, polybutylene terephthalate etc., wherein is preferably polyethylene terephthalate and polybutylene terephthalate.
The used Celanex of the present invention is with neighbour-chlorophenol during as the temperature measuring limiting viscosity of solvent at 35 ℃, and this limiting viscosity is preferably 0.6 to 1.3, more preferably 0.8 to 1.1 scope.If limiting viscosity, will make by the prepared molded object physical strength deficiency of flame retardant resin composition that greater than 1.3, then the flowability of flame-retardant polyester resin composition will reduce, and cause the forming process difficulty as if limiting viscosity less than 0.6.
The usage quantity of used cyanurotriamide modified resol is 5 to 50 weight parts with respect to the Celanex composition in the flame retardant resin composition of the present invention.If usage quantity is during less than 5 weight parts, flame retardant resistance is deficiency, otherwise when usage quantity during greater than 50 weight parts, physical strength will reduce after the moulding.
Red phosphorus usage quantity used in the flame retardant resin composition of the present invention is 2 to 20 weight parts with respect to the Celanex composition.When usage quantity during less than 2 weight parts, flame retardant resistance deficiency, if usage quantity is greater than 20 weight parts, the physical strength after the moulding is bad.
Used red phosphorus can directly use, and is used after red phosphorus being scattered in advance make resin particle in the vector resin.Wherein as the resin of carrier for can and not undermining required final molding product character, the identical resin of Celanex that the use of preferred vector resin is used with (A) composition with the resin of the used Celanex compatibility of the present invention.When red phosphorus is when using with the form of making resin particle, its usage quantity is to make wherein phosphorus content in the above-mentioned red phosphorus scope that defines.
Flame retardant resin composition of the present invention can further add inorganic filler according to circumstances, the weighting agent example comprises for example glass fibre, carbon fiber, mica, lime carbonate, talcum powder, kaolin, nanoclay etc., and its usage quantity is preferably 5 to 100 weight parts with respect to Celanex composition 100 weight parts.
Flame retardant resin composition of the present invention also can further add additives known according to circumstances, comprise for example antioxidant, thermo-stabilizer, lubricant, nucleus agent, look mother and impact modifying agent etc., its content can be any amount of known use, only otherwise influencing the required rerum natura of composition gets final product.
The not halogen-containing and antimonous oxide of flame retardant resin composition of the present invention, however flame-retardant nature had, and have excellent mechanical strength, can be used for making electronics, electric, information, communication and automobile moulding product part.
Embodiment
The present invention will further be illustrated by the following example and comparative example, but disclosed embodiment is only in order to explanation but not in order to limit the scope of the invention.
Each used in the following example and comparative example composition is described as follows:
Polybutylene terephthalate (PBT): limiting viscosity 0.93, for Changchun Artificial Resin Factory Co. Ltd. makes, commodity are called PBT 1100L.
Polyethylene terephthalate (PET): limiting viscosity 0.7, in emerging weaving limited-liability company make.
The pre-mixed resin master batch that contains red phosphorus: red phosphorus content 30%, vector resin are polybutylene terephthalate, and for Japanese phosphorus chemistry company makes, commodity are called PBT 2130.
Cyanurotriamide modified phenol-formaldehyde A: Changchun Artificial Resin Factory Co. Ltd. makes, and commodity are called PF 6300.
Phenolic varnish-phenol resins: Changchun Artificial Resin Factory Co. Ltd., commodity are called PF5110.
Melamine cyanurate: Japanese Nissan (Nissan) chemical industry limited-liability company, commodity are called MC440.
Red phosphorus: Japanese phosphorus chemistry company makes, and commodity are called PX140.
Glass fibre: Taiwan glass industry corporation makes, and commodity are called GF 183E.
Triphenyl: big eight chemical industrial companies of Japan make, and commodity are called PX200.
Cyanurotriamide modified bakelite B: the big Japanese ink chemical industry limited-liability company of Japan makes, and commodity are called KA7755.
Embodiment 1
Mix polybutylene terephthalate 100 weight parts, red phosphorus powder 4 weight parts and cyanurotriamide modified phenol-formaldehyde A 25 weight parts; the ZSE27 twin screw extruder that uses German Leistritz company to make is extruded; forcing machine heating zone temperature range is 240-265 ℃; screw speed is 350rpm; after the resin streak of extruding (strand) imports the tank cooling, with the dicing machine granulation.
Resin particle after the granulation is set in 140 ℃ oven for drying 3 hours with temperature, utilizes ejaculator to penetrate again, makes test piece, for follow-up fire retardancy test transitivity test.Test method is as follows:
Fire retardancy test: polyester and resin composition is made the test piece that thickness is 1.6 millimeters and 0.8 millimeter, tests its flame retardant resistance according to the UL94 specification.Get 5 test pieces that same combination is made, every burning 2 times adds up to 10 total combustion times to be no more than 50 seconds and the single burning is no more than 10 seconds and promptly represents to pass through combustion test.
Tensile strength test: polyester and resin composition is made the dumbbell shape test piece of about 127mm * 12.7mm * 3.2mm, tests with INSTRON 4467 type universal testing machines according to ASTM D638 standard.
The flexural strength test: polyester and resin composition is made the test piece of about 127mm * 12.7mm * 6.4mm, tests with INSTRON 4467 type universal testing machines according to ASTM D790 standard.
Separate out evaluation test: polyester and resin composition is made colour table, place 140 ℃ of baking ovens, take out after 7 days, observe the test piece outward appearance, if the surface has membranoid substance then to represent to separate out phenomenon.
Embodiment 2-7
As method as described in the embodiment 1, make resin particle according to following table 1 listed composition.And carry out fire-retardant transitivity according to the method described above and test.The results are shown in following table 2.For ease of relatively, simultaneously the composition of the foregoing description 1 is listed in table 1 and 2 together.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | |
| Polybutylene terephthalate | 100 | 100 | 100 | 100 | 100 | 100 | - |
| Polyethylene terephthalate | - | - | - | - | - | - | 100 |
| Glass fibre | - | - | 62 | 62 | 62 | 62 | 62 |
| Red phosphorus | 4 | - | - | - | - | - | - |
| Red phosphorus pre-mixed resin grain | - | 18 | 25 | 25 | 65 | 30 | 25 |
| Cyanurotriamide modified phenol-formaldehyde A | 25 | 25 | 15 | 40 | 15 | - | 15 |
| Cyanurotriamide modified bakelite B | - | - | - | - | - | 15 | - |
Table 2
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | |
| UL94 (1.6 millimeters) | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
| UL94 (0.8 millimeter) | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
| Combustion time (second) | 25 | 26 | 32 | 23 | 28 | 31 | 35 |
| Tensile strength (kg/cm 2) | 602 | 576 | 1298 | 1175 | 1300 | 1275 | 1450 |
| Flexural strength (kg/cm 2) | 920 | 890 | 1900 | 1750 | 1950 | 1875 | 2100 |
| Separate out situation | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have |
By The above results as can be known, flame-retardant polyester resin composition of the present invention not only has excellent mechanical intensity, simultaneously can be by the flame retardant resistance test of UL94, and appearance is also good and do not have a situation of separating out.Especially use the cyanurotriamide modified phenol-formaldehyde A of red phosphorus pre-mixed resin grain, 62 weight part glass fibre, 15 weight parts of 25 weight parts and the polybutylene terephthalate of 100 weight parts among the embodiment 3, it mixes in the forcing machine kneading, resulting composition not only can reach the flame retardant resistance of UL94 0.8mm V-0, has good mechanical strength simultaneously.And because that the fire-retardant mechanism of phosphorus flame retardant is mainly solid phase is fire-retardant, therefore when burning, form carburization zone in conjunction with foaming and the cyanurotriamide modified resol of solid-phase carbon source and the fire-retardant combination of red phosphorus with even bubble, can effectively block inflammable gas and overflow, thereby reach splendid flame retardant effect.
Comparative example 1 to 5
As method as described in the embodiment 1, make resin particle according to following table 3 listed compositions.And carry out fire-retardant transitivity according to aforesaid method and test.The results are shown in following table 4.
Table 3
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |
| Polybutylene terephthalate | 100 | 100 | 100 | 100 | 100 |
| Glass fibre | 62 | 62 | 62 | 62 | 62 |
| Red phosphorus pre-mixed resin grain | 10 | 30 | 25 | 25 | -- |
| Triphenyl | -- | -- | -- | -- | 20 |
| Cyanurotriamide modified phenol-formaldehyde A | 25 | 10 | -- | -- | 15 |
| Phenolic varnish-phenol resins | -- | -- | 15 | 15 | -- |
| Melamine cyanurate | -- | -- | -- | 10 | -- |
Table 4
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |
| UL94 (1.6 millimeters) | V-1 | V-1 | V-0 | V-0 | V-0 |
| UL94 (0.8 millimeter) | V-2 | V-2 | V-0 | V-0 | V-2 |
| Combustion time (second) | -- | -- | 48 | 35 | - |
| Tensile strength (kg/cm 2) | -- | -- | 1210 | 1180 | 900 |
| Flexural strength (kg/cm 2) | -- | -- | 1900 | 1750 | 1300 |
| Separate out situation | Do not have | Do not have | Do not have | Do not have | Have |
By The above results as can be known, the resin combination of comparative example 1 is because contained red phosphorus content is lower than the scope that the present invention defines, so the flame retardant resistance deficiency.Though simultaneously in the resin combination of comparative example 2 red phosphorus content in the scope that the present invention defined, the quantity not sufficient of contained cyanurotriamide modified resol, so flame retardant resistance is also not enough.
In addition, the resin combination of comparative example 3 uses the polybutylene terephthalate of 15 weight part phenolic varnish-phenol resins, 25 weight part red phosphorus pre-mixed resin grains, 62 weight part glass fibre and 100 weight parts, though it can reach the flame retardant resistance of UL94 V-0, but its flame retardant resistance test is too critical, because of rather than fine.The resin combination of comparative example 4 uses 25 weight part red phosphorus pre-mixed resin grains, 62 weight part glass fibre, 15 weight part phenolic varnish-phenol resins, 10 weight part melamine cyanurate and 100 weight part polybutylene terephthalates, though it can effectively reduce combustion time, but the rerum natura of resin combination reduces, and because the apparent specific gravity too little (0.1 to 0.3) of melamine cyanurate, pan feeding difficulty in extrusion is difficult for disperseing in composition.
Use the cyanurotriamide modified resol of 20 weight part phosphoric acid ester, 62 weight part glass fibre, 15 weight parts and the polybutylene terephthalate of 100 weight parts in the comparative example 5, not only phenomenon is separated out on flame retardant resistance and physical strength deficiency and surface for it.
Can find out that by The above results flame-retardant polyester resin composition of the present invention not only has excellent flame retardancy, have excellent physical strength simultaneously.
Claims (7)
1. flame-retardant polyester resin composition comprises: (A) Celanex resin 100 weight parts, (B) cyanurotriamide modified resol 5 to 50 weight parts, and (C) red phosphorus 2 to 20 weight parts.
2. flame-retardant polyester resin composition as claimed in claim 1, wherein this Celanex resin be by aromatic dicarboxylic acid or its ester as sour composition and aliphatic diol or its ester as the polyester of pure composition through the reaction gained.
3. flame-retardant polyester resin composition as claimed in claim 2, wherein this Celanex resin is selected from polyethylene terephthalate, poly-naphthalene diformic acid dimethyl ester, polybutylene terephthalate.
4. flame-retardant polyester resin composition as claimed in claim 1 wherein also comprises inorganic filler.
5. flame-retardant polyester resin composition as claimed in claim 4, wherein this inorganic filler is selected from glass fibre, carbon fiber, mica, lime carbonate, talcum powder, kaolin, nanoclay.
6. flame-retardant polyester resin composition as claimed in claim 4, wherein this inorganic filler usage quantity is 5 to 100 weight parts with respect to 100 weight part Celanex compositions.
7. flame-retardant polyester resin composition as claimed in claim 1 wherein also comprises the additive that is selected from antioxidant, thermo-stabilizer, lubricant, nucleus agent, look mother and impact modifying agent.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02142242 CN1209414C (en) | 2002-08-27 | 2002-08-27 | Fire retardant polyester resin composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02142242 CN1209414C (en) | 2002-08-27 | 2002-08-27 | Fire retardant polyester resin composition |
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| CN1478814A CN1478814A (en) | 2004-03-03 |
| CN1209414C true CN1209414C (en) | 2005-07-06 |
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| CN101260227B (en) * | 2008-04-24 | 2012-05-23 | 同济大学 | Method for preparing halogen-free flame-proof polylactic acid |
| CN103073856A (en) * | 2012-12-26 | 2013-05-01 | 浙江大学宁波理工学院 | Phenyl phosphonic acid rare-earth salt compounded system flame-retardant glass fiber enhanced PET material and preparation method thereof |
| CN109777052A (en) * | 2019-01-07 | 2019-05-21 | 宏秀电气有限公司 | One or two fusion device shell body materials |
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