CN100341940C - Prepn of polyformaldehyde material with polyurethane-base composite fire retardant - Google Patents
Prepn of polyformaldehyde material with polyurethane-base composite fire retardant Download PDFInfo
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- CN100341940C CN100341940C CNB2006100204324A CN200610020432A CN100341940C CN 100341940 C CN100341940 C CN 100341940C CN B2006100204324 A CNB2006100204324 A CN B2006100204324A CN 200610020432 A CN200610020432 A CN 200610020432A CN 100341940 C CN100341940 C CN 100341940C
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Abstract
The present invention relates to a preparation method of a fire-retardant polyformaldehyde material of polyurethane base composite fire retardant, which is characterized in that the method comprises the following steps that (1) 10 to 80 parts by weight of flame retardant, 10 to 50 parts by weight of thermoplastic polyurethane resin (TPU) and 0 to 50 parts by weight of flame-retardant potentiating agent are melted and compounded in a mixer and banbury mixer or an extruding machine under the temperature of 150 to 240 DEG, so particles of the flame retardant can be coated by the TPU resin, the polyurethane base composite fire retardant can be obtained by the preparation, and the composite fire retardant is pulverized into powder or pelleted into particle material; (2) 20 to 50 parts by weight of the polyurethane base composite fire retardant, 50 to 100 parts by weight of polyformaldehyde and 0.1 to 1 parts by weight of anti-oxidant are thoroughly mixed and are melted to extrude and granulate in the extruding machine under the temperature of 170 to 230 DEG, and fire retardant polyoxymethylene material can be obtained.
Description
Technical field
The present invention relates to a kind of preparation method of polyformaldehyde material with polyurethane-base composite fire retardant, belong to the preparation field of flame-proofed polymer material.
Background condition
Polyoxymethylene (POM) is a kind of important engineering plastics, has good mechanical property, electrical property, advantages of good abrasion, resistance to fatigue and self lubricity, and dimensional stability is good, is widely used in numerous areas such as automobile, electric, precision optical machinery and building materials.But the POM limiting oxygen index(LOI) only has 15, is the most incendive plastics variety, has limited it and has used, and in order to improve the flame retardant properties of POM, the realistic meaning of developing fire-retardant POM is great.
POM is fire-retardant to be a worldwide problem, because the POM poor heat stability, the rapid depolymerization of being heated is a formaldehyde, and oxidation of formaldehyde product formic acid further promotes the POM thermal-oxidative degradation again, produces a large amount of inflammable gass.In addition, POM belongs to the line style high crystallinity polymer, and is poor with other material compatibility, directly adds fire retardant and is difficult to the good fire-retardant POM of processability.U.S. Pat P 6699923 has reported employing encapsulated red phosphorus and the fire-retardant POM technology of char-forming agent, but complicated process of preparation, cost height, difficult industrial applications.It is main flame retardant that Japanese Patent JP 204 167 adopts P contained compound, and aromatic compound or nitrogenous compound have made flame retardant properties POM preferably as retardant synergist, but mechanical properties decrease is serious.The difficult point that direct interpolation fire retardant prepares fire-retardant POM is that the consistency of fire retardant and resin is poor, and the fire retardant difficulties in dispersion is difficult to obtain ideal phase farmland size, thereby causes flame retarding efficiency lower, the serious deterioration of mechanical property.Therefore solve that consistency and dispersion problem are the gordian techniquies of the good fire-retardant POM of processability between fire retardant and the POM.
Summary of the invention
The objective of the invention is provides a kind of polyformaldehyde material with polyurethane-base composite fire retardant preparation method at the deficiencies in the prior art.Be characterized in adopting with the POM consistency preferably compound obtain of TPU and fire retardant and retardant synergist with TPU utilize the fire-retardant POM material of this fire retardant and the compound preparation of POM fusion again for " shell " fire retardant is the cladded type composite flame-retardant agent of " core ".
Heat plasticity polyurethane elastic body (TPU) is the polymer materials of being found at present best with the POM consistency.Compound by fusion, TPU can be dispersed in the POM matrix, forms comparatively ideal phase farmland size, thereby effectively absorbs impact energy, increases substantially polyoxymethylene toughness, so TPU is at present generally as the POM anti-impact modifier.The amidine functional group that contains some amount in addition among the TPU can effectively absorb materials such as formic acid that the POM thermolysis discharges, formaldehyde, therefore can improve the thermostability of POM, and TPU self has certain one-tenth charcoal, therefore has a positive effect to its POM is fire-retardant.
Purpose of the present invention is realized that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
1. the preparation method of polyformaldehyde material with polyurethane-base composite fire retardant:
(1) preparation of polyurethane-base composite flame-retardant agent
With polyether-type or polyester type TPU(Thermoplastic polyurethanes) 10-50 weight part and fire retardant 20-80 weight part, retardant synergist 0-50 weight part carries out fusion in mixing roll, Banbury mixer or the forcing machine of 150 ℃-240 ℃ of temperature compound, realize the coating of urethane resin to flame retardant particle, prepare the polyurethane-base composite flame-retardant agent, above-mentioned composite flame-retardant agent is ground into or pelletizing powdered or pellet;
(2) preparation of polyformaldehyde material with polyurethane-base composite fire retardant
With kematal or homopolymerization polyoxymethylene 50-100 weight part, polyurethane-base composite flame-retardant agent 20-50 weight part and oxidation inhibitor 0.1-1 weight part thorough mixing melt extrude granulation in temperature 170-230 ℃ forcing machine, obtain fire-retardant polyformaldehyde material.
Fire retardant is at least a in melamine cyanurate, melamine polyphosphate, melamine phosphate, decabromodiphenyl oxide, octa-BDE, tetrabromo-bisphenol, ammonium polyphosphate, microcapsule red phosphorus, the magnesium hydroxide.
At least a in the trimeric cyanamide that cooperates above-mentioned fire retardant to use together, tetramethylolmethane, triphenylphosphate, the antimonous oxide of retardant synergist.
Oxidation inhibitor is antioxidant 1010 or oxidation inhibitor 245, and oxidation inhibitor is to well known to a person skilled in the art technology, can be used, and its precondition is that these oxidation inhibitor are realized the object of the invention and obtaining of excellent results of the present invention do not have a negative impact.
Experiment shows, employing is with melamine cyanurate, polyether-type thermoplastic polyurethane and the M90 of skies limited-liability company copolymerized methanal are the polyurethane-base composite fire retardant polyoxymethylene that feedstock production obtains, when the composite flame-retardant agent addition is 35%, Flame Retardancy can reach the UL94-V1 level, and the material notched Izod impact strength reaches 7.7kJ/m
2, and adopt the melamine cyanurate and the M90 copolymerized methanal of same amount directly compound, and the fire-retardant polyoxymethylene that obtains then can not be tested by UL94, and its notched Izod impact strength is near or below 5kJ/m
2
The present invention has following advantage:
(1) fire retardant be dispersed in TPU mutually in and directly do not contact with POM, but can evenly spread in the POM matrix, thereby obtain flame retardant properties and mechanical property excellent fire retardant POM material with the TPU resin.
(2) adopt TPU base composite fire retardant polyoxymethylene, problem such as it is poor to have solved among the conventional preparation method fire retardant and polyoxymethylene consistency, and dispersing uniformity is not good enough, dispersed phase size is big can realize fire retardant ultra-fine homodisperse in resin.
(3) urethane can improve the polyoxymethylene heat decomposition temperature, self has better carbon-forming performance, can further improve the polyoxymethylene flame retardant properties.
Embodiment
Below by embodiment the present invention is carried out concrete description.Be necessary to be pointed out that at this following examples only are used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to the invention described above content.
Embodiment 1: with 20kg melamine cyanurate and 10kg polyether-type thermoplastic polyurethane, and compound extruding pelletization in the twin screw extruder of 160 ℃ of temperature, being ground into median size after the extrudate cooling is 0.3cm.With above-mentioned composite flame-retardant agent pellet 40kg, after kematal 100kg and the oxidation inhibitor 245 1g solid phase mixing, extruding pelletization in temperature 170-190 ℃ forcing machine obtains fire-retardant polyoxymethylene.The flame retardant properties of this product reaches the UL94-V2 rank, and limiting oxygen index(LOI) reaches 26, and the material notched Izod impact strength reaches 7.3kJ/m
2
Embodiment 2: with the 40kg ammonium polyphosphate, and 1kg tetramethylolmethane and 30kg polyester type thermoplastic polyurethane, mixing 20 clocks in the Banbury mixer of 180 ℃ of temperature are ground into median size 0.5mm product after the cooling.After above-mentioned composite flame-retardant agent powder 20kg, 50kg homopolymerization polyoxymethylene and oxidation inhibitor 245 0.5g solid phase mixing, extruding pelletization in temperature 180-200 ℃ forcing machine obtains fire-retardant polyoxymethylene.This product flame retardant properties reaches the UL94-V1 level, and limiting oxygen index(LOI) reaches 28, and the material notched Izod impact strength reaches 7.2kJ/m
2
Embodiment 3: with the 60kg decabromodiphenyl oxide, 20kg antimonous oxide and 50kg polyether-type thermoplastic polyurethane compoundly in temperature 170-210 ℃ forcing machine are extruded, pelletizing.With above-mentioned composite flame-retardant agent pellet 50kg, after homopolymerization polyoxymethylene 80kg and the antioxidant 1010 1g solid phase mixing, extruding pelletization in temperature 190-200 ℃ forcing machine obtains fire-retardant polyoxymethylene.The flame retardant properties of this product reaches the UL94-V2 level, and limiting oxygen index(LOI) reaches 27, and the material notched Izod impact strength reaches 6.8kJ/m
2
Embodiment 4: with 40kg microcapsule red phosphorus, 20kg magnesium hydroxide, 15kg trimeric cyanamide and polyether-type thermoplastic polyurethane 30kg after 10 minutes, are ground into the product of median size 0.8cm at the mixer mixing of 200 ℃ of temperature.After above-mentioned composite flame-retardant agent pellet 40kg and homopolymerization polyoxymethylene 70kg and antioxidant 1010 0.8g solid phase mixing, extruding pelletization in temperature 170-190 ℃ forcing machine obtains fire-retardant polyoxymethylene.The flame retardant properties of this product reaches the UL94-V2 rank, and limiting oxygen index(LOI) reaches 25, and the material notched Izod impact strength reaches 7.0kJ/m
2
Embodiment 5: with the 50kg melamine phosphate, and the 20kg tetramethylolmethane, 10kg trimeric cyanamide and polyester type thermoplastic polyurethane 15kg after 40 minutes, are ground into the product that median size is 0.1cm at two roller mill mixings of 160 ℃ of temperature.With above-mentioned composite flame-retardant agent pellet 35kg, after kematal 65kg and the oxidation inhibitor 2450.6g solid phase mixing, extruding pelletization in temperature 170-190 ℃ forcing machine obtains fire-retardant polyoxymethylene.The flame retardant properties of this product reaches the UL94-V1 rank, and limiting oxygen index(LOI) reaches 28, and the material notched Izod impact strength reaches 7.5kJ/m
2
Claims (3)
1. the preparation method of polyformaldehyde material with polyurethane-base composite fire retardant is characterized in that this method contains following steps:
(1) preparation of polyurethane-base composite flame-retardant agent
With polyether-type or polyester type TPU(Thermoplastic polyurethanes) 10-50 weight part, fire retardant 20-80 weight part and retardant synergist 0-50 weight part, it is compound to carry out fusion in mixing roll, Banbury mixer or the forcing machine of 150 ℃-240 ℃ of temperature, realize the coating of urethane resin to flame retardant particle, prepare the polyurethane-base composite flame-retardant agent, above-mentioned composite flame-retardant agent is ground into powder or pelletizing becomes pellet;
(2) preparation of polyformaldehyde material with polyurethane-base composite fire retardant
With kematal or homopolymerization polyoxymethylene 50-100 weight part, polyurethane-base composite flame-retardant agent 20-50 weight part and oxidation inhibitor 0.1-1 weight part thorough mixing melt extrude granulation in temperature 170-230 ℃ forcing machine, obtain fire-retardant polyformaldehyde material.
2. the preparation method of polyformaldehyde material with polyurethane-base composite fire retardant according to claim 1 is characterized in that fire retardant is at least a in melamine cyanurate, melamine polyphosphate, melamine phosphate, decabromodiphenyl oxide, octa-BDE, tetrabromo-bisphenol, ammonium polyphosphate, microcapsule red phosphorus, the magnesium hydroxide;
3. the preparation method of polyformaldehyde material with polyurethane-base composite fire retardant according to claim 1 is characterized in that retardant synergist is at least a in trimeric cyanamide, tetramethylolmethane, triphenylphosphate and the antimonous oxide.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100204324A CN100341940C (en) | 2006-03-08 | 2006-03-08 | Prepn of polyformaldehyde material with polyurethane-base composite fire retardant |
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| CNB2006100204324A CN100341940C (en) | 2006-03-08 | 2006-03-08 | Prepn of polyformaldehyde material with polyurethane-base composite fire retardant |
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| CN1810881A CN1810881A (en) | 2006-08-02 |
| CN100341940C true CN100341940C (en) | 2007-10-10 |
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| CN101851351A (en) * | 2010-06-29 | 2010-10-06 | 四川大学 | Inorganic hydroxide composite flame retardant and high-performance halogen-free flame-retardant polyformaldehyde material using same for antiflaming |
| CN102061057B (en) * | 2010-12-20 | 2012-09-05 | 四川大学 | Halogen-free expanded flame-retardant polyformaldehyde composite material and preparation method thereof |
| CN104650534A (en) * | 2015-02-28 | 2015-05-27 | 秦富英 | Expansive type flame-retardant polyformaldehyde composition |
| CN105860422A (en) * | 2016-04-25 | 2016-08-17 | 苏州亚科塑胶有限公司 | High-performance polyformaldehyde composite material and preparation method thereof |
| CN105820503A (en) * | 2016-05-16 | 2016-08-03 | 苏州新区华士达工程塑胶有限公司 | Modified polyformaldehyde inflaming retarding plastic |
| CN106633805A (en) * | 2016-12-30 | 2017-05-10 | 江苏钟山化工有限公司 | Preparation method of solid flame retardant for polyurethane and solid flame retardant prepared by method |
| CN109867905B (en) * | 2017-12-01 | 2022-07-12 | 万华化学集团股份有限公司 | POM/TPU alloy material with low VOC content and preparation method thereof |
| CN111944286B (en) * | 2020-08-14 | 2022-08-02 | 毛澄宇 | Polylactic acid modified material for 3D printing and preparation method and application thereof |
| CN112250988B (en) * | 2020-10-19 | 2023-01-24 | 中国五环工程有限公司 | High-performance polyformaldehyde composite material and preparation method thereof |
| CN112321988B (en) * | 2020-11-09 | 2022-05-06 | 金发科技股份有限公司 | High glow wire polyformaldehyde composition and preparation method and application thereof |
| CN112625331B (en) * | 2020-12-08 | 2023-04-14 | 江苏达胜高聚物股份有限公司 | Flame-retardant PE cable material and preparation method and application thereof |
| CN112662118A (en) * | 2020-12-09 | 2021-04-16 | 上海普利特复合材料股份有限公司 | Halogen-free flame-retardant ABS resin composition containing nano-scale flame retardant and preparation method thereof |
| CN112646308A (en) * | 2020-12-09 | 2021-04-13 | 浙江普利特新材料有限公司 | Halogen-free flame-retardant high-toughness ABS resin composition containing nano-scale flame retardant and preparation method thereof |
| CN112552636A (en) * | 2020-12-09 | 2021-03-26 | 重庆普利特新材料有限公司 | Halogen-free flame-retardant self-extinguishing ABS resin containing nanoscale flame retardant and preparation method thereof |
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| CN1810881A (en) | 2006-08-02 |
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