CN107778527A - A kind of halogen-free flameproof compound system based on phosphorus aluminium compound and its application in fiberglass reinforced engineering plastics - Google Patents
A kind of halogen-free flameproof compound system based on phosphorus aluminium compound and its application in fiberglass reinforced engineering plastics Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
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- 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
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
Abstract
The invention discloses a kind of halogen-free flameproof compound system based on phosphorus aluminium compound, gross weight is 100% meter, and raw material composition includes：Diethyl hypo-aluminum orthophosphate 40~90%；Organic phosphorous acid aluminium 10~50%；Zinc salt heat-stable compound 1~10%；Described organic phosphorous acid aluminium, shown in structural formula such as following formula (I), in formula, R is selected from the straight chain fatty saturated hydrocarbyl that carbon number is 1~6, carbon number is 1~6 straight chain fatty unsaturated alkyl or aromatic radical.The invention discloses a kind of new halogen-free flameproof compound system based on phosphorus aluminium compound, the halogen-free flameproof compound system has the characteristics that high fire-retardance, non-migratory, not etching apparatus.It can be applied in fiberglass reinforced engineering plastics, obtain halogen-free flame-retardant glass fiber enhancement engineering plastic material, for preparing the part or product of field of electronics.
Description
Technical field
The present invention relates to the technical field of halogen-free flame retardants, and in particular to a kind of halogen-free flameproof based on phosphorus aluminium compound is answered
Application with system and its in flame-proof glass fibre enhancement engineering plastics.
Background technology
Fiberglass reinforced engineering plastics (such as various nylon, polyester) are because with good rigidity and impact resistance, low warpage
The performance characteristics such as property, high dimensional stability, good appearance and be widely used in field of electronics.In these necks
The application in domain, proposes fire-retardant requirement to material, and engineering plastics are combustible materials mostly, with glass it is compound after, due to
The wick effect of glass so that fiberglass reinforced engineering plastics are easier to burn.Therefore fiberglass reinforced engineering plastics are in these fields
Using when, it is necessary to solve the problems, such as fire-retardant, and the presence of wick effect make it that its fire-retardant difficulty is bigger.
At present, for the fire-retardant of fiberglass reinforced engineering plastics, the basic flame-retardant system of two classes is included：Halogen system flame-retardant system
With non-halogen fire-retardant system.Halogen system flame-retardant system is typically brominated flame-retardant collaboration antimony oxide, and numerous studies show, are added with
The fiberglass reinforced engineering plastics of bromide fire retardant can produce thick smoke and the harmful substance such as hydrogen bromide in burning, human body can be caused to stop up
Breath.Therefore, developing safe and environment-friendly, halogen-free flame-retardant system for fiberglass reinforced engineering plastics turns into the focus of research, occurs in recent years
The new halogen-free flame retardants or flame-retardant system applied to fiberglass reinforced engineering plastics.
According to the literature, the halogen-free flame retardants applied to fiberglass reinforced engineering plastics mainly includes two major class primary structures：
One kind is red phosphorus；Another kind of is phosphorus nitrogen system flame-retardant system.For red phosphorus, although its good flame retardation effect, it faces two problems：
First, the color of red phosphorus, limits its application, it is generally only to apply in black products；It is second, easy in process
The violents in toxicity such as hydrogen phosphide are produced, bring environmental protection and safety problem, therefore red phosphorus is not the optimal choosing of fiberglass reinforced engineering plastics
Select.For phosphorus nitrogen system flame-retardant system, this is a kind of efficient flame-retardant system, has high flame retarding efficiency, it also avoid red phosphorus
Some defects, it is the focus studied at present.With the most use, the phosphorus nitrogen compound ligand based on diethyl hypo-aluminum orthophosphate is answered at present
System, for example, diethyl hypo-aluminum orthophosphate compounds melamine Quadrafos (MPP) system, due to higher phosphorus content, and
The synergy of phosphorus nitrogen, it is possible to achieve to the highly effective flame-retardant of fiberglass reinforced engineering plastics, also in the absence of product color problem, simultaneously
With very high decomposition temperature, in the high temperature working processes of fiberglass reinforced engineering plastics, the hypertoxic gas such as hydrogen phosphide will not be produced.
But for the phosphorus nitrogen compound system based on diethyl hypo-aluminum orthophosphate, however it remains some shortcomings, be mainly manifested in：First, two kinds of groups
Divide and certain reaction decomposition is had in high temperature, produce a small amount of sour gas, these sour gas can be to the gold of process equipment
Belong to part and produce corrosion, need to change part after a certain time, the problem of bringing the increase of cost and reduce production efficiency；Two
It is that nitrogen-containing compound MPP has certain precipitation, material is in injection molding process, after being molded the product of certain modulus, in mould
There can be deposit on tool, the presence of these deposits can influence the outward appearance of product, and this is to need cleaning mould of stopping work, and can also be dropped
Low production efficiency, while this precipitation can also cause fire retardant to be migrated to product surface, cause fire retardant skewness and loss,
, potential safety hazard be present in the final fire-retardant failure for causing material.
As a whole, it is applied to the flame-retardant system of fiberglass reinforced engineering plastics at present, there are color, has poison gas
Body, easily separate out and have the problems such as corrosion, some are that fatal problem can not then use, and some are then to cause cost increase, efficiency drop
It is low.Therefore, it is necessary to develop new halogen-free flame-retardant system.
The content of the invention
The present invention is for the existing compounding of the phosphorus nitrogen based on diethyl hypo-aluminum orthophosphate applied to fiberglass reinforced engineering plastics
The defects of flame-retardant system, develop the new halogen-free flameproof compound system based on phosphorus aluminium compound, the halogen-free flameproof compound system
There is high fire-retardance, non-migratory, not etching apparatus.It can be applied in fiberglass reinforced engineering plastics, obtain halogen-free flame-retardant glass
Fine enhancement engineering plastic material, for preparing the part or product of field of electronics.
Specific technical scheme is as follows：
A kind of halogen-free flameproof compound system based on phosphorus aluminium compound, gross weight are 100% meter, and raw material composition includes：
Diethyl hypo-aluminum orthophosphate 40~90%；
Organic phosphorous acid aluminium 10~50%；
Zinc salt heat-stable compound 1~10%.
The present invention uses diethyl hypo-aluminum orthophosphate, then passes through the organic phosphorous acid aluminum and zinc salt non-migratory with special high temperature resistant
Heat-stable compound cooperates with, and forms the collaboration compounding flame retardant based on organophosphor constructed of aluminium, solves existing fiberglass reinforced engineering
The defects of plastics halogen-free flame-retardant system is perishable, precipitation easy to migrate.
The present invention will be elaborated below.
The present invention is to solve various existing for the existing halogen-free flame-retardant system being applied in fiberglass reinforced engineering plastics lack
For the purpose of falling into, inventor has made extensive and intensive studies.For the existing compositional flame-retardant body based on diethyl hypo-aluminum orthophosphate
The problem of flame-proof glass fibre enhancement engineering plastics are present is tied up to, has investigated new flame-retardant system, as a result finds diethyl hypo-aluminum orthophosphate
Organic phosphorous acid aluminium, and zinc salt heat-stable compound is cooperateed with to solve this problem well.
Shown in the chemical constitution of diethyl hypo-aluminum orthophosphate such as following formula (II)：
Diethyl hypo-aluminum orthophosphate is characterized in phosphorus content height, good flame resistance, has higher temperature of initial decomposition, water-soluble
Low, resistance to migration is nonhygroscopic, and more application is in the engineering plastics such as nylon, PBT at present, particularly engineering plastics of fiberglass reinforced
In.Be used alone diethyl hypo-aluminum orthophosphate, in the absence of separate out the problem of, but its fire resistance deficiency, therefore also need to it is nitrogenous
MPP compounding, can be only achieved fire-retardant ask.The flame-retardant system in fiberglass reinforced engineering plastics is applied at present substantially with diethyl
Aluminum phosphate cooperates with MPP systems.
But when with MPP compounding uses, its decomposition temperature can reduce diethyl hypo-aluminum orthophosphate, can be discharged in process
Sour gas and ammonia, process equipment metal parts can be produced and corroded, and MPP migration characteristic so that die surface is present
Deposit, outward appearance is influenceed, it is necessary to which periodic cleaning mould, reduces production efficiency.It will be apparent that there are problems that for MPP is to cause these
Key, as far as possible reduce MPP use or without using MPP.
Inventor is had found by studying, and in the presence of diethyl hypo-aluminum orthophosphate, adds suitable organic phosphorous acid
Aluminium, the flame-retardant system based on organophosphor constructed of aluminium is formed, the system has preferable flame-retarding characteristic.
Described organic phosphorous acid aluminium, shown in structural formula such as following formula (I)：
In formula, R be selected from carbon number be 1~6 straight chain fatty saturated hydrocarbyl, carbon number be 1~6 straight chain fatty unsaturated alkyl
Or aromatic radical.Preferably, described R is methyl or ethyl, the molecular weight of R group is smaller, and phosphorus content is higher, more has to fire-retardant
Profit.
Described organic phosphorous acid aluminium is prepared by following method：
(1) using organic phosphite as raw material, organic phosphorous acid is obtained after hydrolyzed under acidic conditions；
(2) organic phosphorous acid prepared by step (1) is mixed with aluminum contained compound, under acid condition, aqueous medium, 0~
After 300 DEG C of reactions, then post-treated obtain described organic phosphorous acid aluminium.
, can be by forming acid condition after acidic materials are mixed with water in step (1), described acidic materials include
Phosphoric acid etc..
Described organic phosphite is selected from methyl-phosphoric acid dimethyl ester, ethyl phosphonic acid dimethyl ester, phosphenylic acid dimethyl ester etc.；
Described hydrolysis is carried out at 150~180 DEG C.
In step (2), described aluminum contained compound be selected from metallic aluminium, aluminium alloy, the oxide of aluminium, aluminium peroxide,
The hydroxide or aluminium salt of aluminium；Described aluminium salt is the aluminium salt of the vapour pressure anion higher than organic phosphorous acid, including aluminium
In carbonate, percarbonate, formates, acetate, propionate, stearate, lactate, ascorbate, oxalates extremely
Few one kind.
Described organic phosphorous acid and the mol ratio of aluminum contained compound are 3:2；Described organic phosphorous acid and mole of water
Than for 1:2.
In step (2), described reaction temperature is preferably 50~170 DEG C, and the reaction time is preferably 1min~100h, reaction
Pressure is preferably 10Pa~10MPa.
In step (2), described post processing is specially：
Reacted suspension is filtered, washed and dried, then is crushed to certain particle diameter.
Described organic phosphorous acid aluminium has very high heat decomposition temperature, can be acted synergistically with diethyl hypo-aluminum orthophosphate, together
When water solubility it is low, resistance to migration.Diethyl hypo-aluminum orthophosphate compounds with organic phosphorous acid aluminium, can solve precipitation and asking in mold deposits
Topic.
Moreover, it has been found that introducing the zinc salt heat-stable compound that a small amount of high temperature resistant does not separate out in above-mentioned system, one can be entered
Step raising is corrosion-resistant, and improves anti-flammability, there is not yet the problem of precipitation.
Preferably, described zinc salt heat-stable compound, selected from least one of Firebrake ZB, zinc oxide, zinc stannate.
Zinc salt heat-stable compound without the crystallization water has high decomposition temperature, water-soluble low, not migration precipitation.Can be with organophosphor
Constructed of aluminium cooperates with, and improves anti-flammability, and with suppression cigarette effect, reduce smoke density.
Further preferably：
Described diethyl hypo-aluminum orthophosphate is white powder, average grain diameter 20<D50<50μm；
Described organic phosphorous acid aluminium is white powder, average grain diameter 20<D50<50μm.
Described zinc salt heat-stable compound is white powder, average grain diameter 20<D50<50μm.
Above-mentioned each powder material uses identical particle size range, is easy to several powders uniformly to mix.
The invention also discloses a kind of halogen-free flame-retardant glass fiber enhancement engineering plastics, using described based on phosphorus aluminium compound
Halogen-free flameproof compound system.
By weight percentage, the raw material composition of described halogen-free flame-retardant glass fiber enhancement engineering plastics includes：
Described base material is selected from nylon or polyester.
Preferably, described halogen-free flameproof compound system accounts for the 15~20% of raw material gross weight；
The raw material composition of the halogen-free flameproof compound system includes：
Diethyl hypo-aluminum orthophosphate 75~80%；
Organic phosphorous acid aluminium 15~20%；
Zinc salt heat-stable compound 5~10%.
Further preferably, described organic phosphorous acid aluminium is methylisothiouronium methylphosphite aluminium, i.e., in formula (I), R is methyl.
Described nylon includes the high-temperature nylons such as fatty polyamide, semiaromatic polyamide composition, preferably, being selected from nylon
6th, at least one of nylon66 fiber, nylon MXD 6, nylon 6T；
Preferably, described polyester is selected from polyethylene terephthalate or polybutylene terephthalate (PBT).
, it is necessary to which halogen-free flame-retardant system is dispersed in matrix when preparing described halogen-free flame-retardant glass fiber enhancement engineering plastics
In material.Particular by band plus the double screw extruder of glass fiber opening and fire retardant powder charging aperture, made through melt blending, extrusion
It is prepared after grain.
Compared with prior art, the invention has the advantages that：
It is provided by the invention to be formed based on diethyl hypo-aluminum orthophosphate, organic phosphorous acid aluminum and zinc salt heat-stable compound compounding
Halogen-free flameproof compound system there is high fire-retardance, non-migratory, low corrosion equipment；Material system and preparation after optimized
The halogen-free flame-retardant glass fiber enhancing nylon or polyester that technique obtains, can reach UL94V0 (1.6mm) flame-retardant standard, and without analysis
Go out, low corrosion equipment, halogen-free flame-retardant glass fiber enhancing proprietary material can be used as to be applied to electric and electronic field.
Embodiment
Embodiment 1
Halogen-free flameproof compounding flame retardant is applied in glass fiber enhanced nylon, follows these steps and method of testing investigation is fire-retardant
The performance of agent.
(1) mixture of halogen-free flame-retardant system
Stirred in height and the compounding flame retardant each component weighed up in advance by proportioning and other auxiliary agents are added in machine, start high-speed stirring
Mix, stir 10min, complete the mixture of halogen-free flame-retardant system powder, discharging.
(2) extruding pelletization of material
Each area's temperature setting of double screw extruder in predetermined temperature, after temperature stabilization 20min, Buddhist nun is added from hopper
Imperial system, by adding glass fiber opening to add, halogen-free flame-retardant system powder is fed glass by powder charging aperture, starts main frame and feeding
Machine, complete the extruding pelletization of material.The material for having made grain is sent into feed bin by blast system, and dries.
(3) application of material and test
The material dried is molded by injection machine the standard specimen of various testing standard defineds, and carries out correlation
The test of material property.It is primarily upon following performance indications：
It is 1. fire-retardant
According to the test of UL94V0 testing standards.
2. resistance to migration experiment
The Flame-retardant Glass Fiber Reinforced Pa sample that will be prepared, is put into climatic chamber, sets 85 DEG C of temperature, relative humidity
85%, the state of specimen surface of the visual observations after 168 hours.
3. corrosion experiment
One metal derby is set on die head, and high-temperature material passes through 25Kg material granulations in die head and metal block contact, test
The waste of metal afterwards, loss is higher, and corrosion resistance is poorer.If etching extent<0.1% is thought that corrosion is acceptable.
Organic phosphorous acid aluminium in the present embodiment is methylisothiouronium methylphosphite aluminium, and specific preparation method is：
(1) preparation of methyl acid phosphate
600g methyl-phosphoric acid dimethyl esters (DMMP), 120g phosphoric acid, 280g water are hydrolyzed 5 hours at 165 DEG C -175 DEG C, obtained
The methyl acid phosphate of 474g concentration 98%.
(2) preparation of methylisothiouronium methylphosphite aluminium
252g aluminium hydroxides are preset in kneader.474g methyl acid phosphates are added batch-wise thereto under agitation
(98%).Reaction automatically begins to while heat release and subsequent reactions is carried out at 150 DEG C.Continue to react at 150 DEG C
2.5h.Product includes methylisothiouronium methylphosphite aluminium and 0.25wt% unreacted methyl acid phosphate.Yield is 98.8%, the starting point of product
Solve 340 DEG C of temperature.
Energy spectrum analysis is carried out to product, elementary analysis result is as shown in table 1.
Table 1
| Element | Wt% |
| C K | 11.2 |
| O K | 43.7 |
| Al K | 16.9 |
| P K | 28.2 |
Each element content and theoretical amount are very close to showing that prepared compound is methylisothiouronium methylphosphite calorize in table 1
Compound.
Each material and proportioning are shown in Table 2 in embodiment, and resulting testing of materials the results are shown in Table 2.
Embodiment 2
Implementation process is same as Example 1, in addition to the ratio of methylisothiouronium methylphosphite aluminium and zinc stannate adjusts, keeps flame-retardant system
Total amount is constant.Other materials and proportioning are shown in Table 2, and resulting material the results are shown in Table 2.
Embodiment 3
Implementation process is same as Example 1, in addition to the ratio of diethyl hypo-aluminum orthophosphate and methylisothiouronium methylphosphite aluminium adjusts, keeps
Flame-retardant system total amount is constant.Other materials and proportioning are shown in Table 2, and resulting material the results are shown in Table 2.
Embodiment 4
Application of the flame-retardant system in fiber glass reinforced PBT.Material and proportioning are shown in Table 2, and resulting material the results are shown in Table 2.
Comparative example 1
Implementation process is same as Example 1, in addition to without using zinc stannate.Other materials and proportioning are shown in Table 2, resulting
Material the results are shown in Table 2.
Comparative example 2
Implementation process is same as Example 1, in addition to without using methylisothiouronium methylphosphite aluminium.Other materials and proportioning are shown in Table 2, institute
Obtained material the results are shown in Table 2.
Comparative example 3
Implementation process is same as Example 1, in addition to only using diethyl hypo-aluminum orthophosphate.Other materials and proportioning are shown in Table 2,
Resulting material the results are shown in Table 2.
Comparative example 4
Implementation process is same as Example 1, in addition to being compounded using diethyl hypo-aluminum orthophosphate with melamine polyphosphate.
Other materials and proportioning are shown in Table 2, and resulting material the results are shown in Table 2.Table 2
Claims (9)
1. a kind of halogen-free flameproof compound system based on phosphorus aluminium compound, it is characterised in that gross weight is counted for 100%, raw material group
Into including：
Diethyl hypo-aluminum orthophosphate 40~90%；
Organic phosphorous acid aluminium 10~50%；
Zinc salt heat-stable compound 1~10%；
Described organic phosphorous acid aluminium, shown in structural formula such as following formula (I)：
In formula, R is selected from the straight chain fatty saturated hydrocarbyl that carbon number is 1~6, carbon number is 1~6 straight chain fatty unsaturated alkyl or virtue
Perfume base.
2. the halogen-free flameproof compound system according to claim 1 based on phosphorus aluminium compound, it is characterised in that described two
Ethyl hypo-aluminum orthophosphate, average grain diameter 20<D50<50μm.
3. the halogen-free flameproof compound system according to claim 1 based on phosphorus aluminium compound, it is characterised in that described has
Machine aluminium phosphite, average grain diameter 20<D50<50μm.
4. the halogen-free flameproof compound system according to claim 1 based on phosphorus aluminium compound, it is characterised in that described zinc
Salt heat-stable compound, selected from least one of Firebrake ZB, zinc oxide, zinc stannate, average grain diameter 20<D50<50μm.
5. a kind of halogen-free flame-retardant glass fiber enhancement engineering plastics, it is characterised in that use according to Claims 1 to 4 is any
Halogen-free flameproof compound system based on phosphorus aluminium compound.
6. halogen-free flame-retardant glass fiber enhancement engineering plastics according to claim 5, it is characterised in that by weight percentage,
Raw material composition includes：
Described base material is selected from nylon or polyester.
7. halogen-free flame-retardant glass fiber enhancement engineering plastics according to claim 6, it is characterised in that by weight percentage,
The raw material composition of the halogen-free flameproof compound system includes：
Diethyl hypo-aluminum orthophosphate 75~80%；
Organic phosphorous acid aluminium 15~20%；
Zinc salt heat-stable compound 5~10%.
8. halogen-free flame-retardant glass fiber enhancement engineering plastics according to claim 7, it is characterised in that described organic phosphorous acid
Aluminium is methylisothiouronium methylphosphite aluminium.
9. halogen-free flame-retardant glass fiber enhancement engineering plastics according to claim 6, it is characterised in that described nylon is selected from Buddhist nun
At least one of dragon 6, nylon66 fiber, nylon MXD 6, nylon 6T；
Described polyester is selected from polyethylene terephthalate or polybutylene terephthalate (PBT).
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| CN201711221539.XA CN107778527A (en) | 2017-11-22 | 2017-11-22 | A kind of halogen-free flameproof compound system based on phosphorus aluminium compound and its application in fiberglass reinforced engineering plastics |
| PCT/CN2018/113908 WO2019100929A1 (en) | 2017-11-22 | 2018-11-05 | Phosphor aluminium compound-based halogen-free flame retardant compound system and application thereof in glass fiber reinforced engineering plastic |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108795038A (en) * | 2018-06-28 | 2018-11-13 | 浙江大学 | The halogen-free flame-retardant system and its application that the thio hypophosphites of dialkyl group list is cooperateed with inorganic phosphite |
| CN108795039A (en) * | 2018-06-28 | 2018-11-13 | 浙江大学 | The halogen-free flame-retardant system and its application that dialkyl dithio hypophosphites is cooperateed with organic phosphite |
| CN108948430A (en) * | 2018-06-28 | 2018-12-07 | 浙江大学 | The thio hypophosphites of dialkyl group list, the halogen-free flame-retardant system of organic phosphite and nitrogenous compound collaboration and its application |
| CN108948419A (en) * | 2018-08-03 | 2018-12-07 | 张家港市五湖新材料技术开发有限公司 | A kind of preparation method of aluminium phosphorus synergistic fire retardant |
| CN109082116A (en) * | 2018-08-09 | 2018-12-25 | 江苏利思德新材料有限公司 | Thermoplastic polymer or the high-temperature thermal stability method of its compound are improved using alkyl phosphorous acid metal salt |
| CN109181293A (en) * | 2018-08-09 | 2019-01-11 | 浙江大学 | Melamine derivative based flame retardant high-temperature thermal stability method and products thereof and application are improved using inorganic and alkyl phosphorous acid metal salt |
| WO2019100929A1 (en) * | 2017-11-22 | 2019-05-31 | 江苏利思德新材料有限公司 | Phosphor aluminium compound-based halogen-free flame retardant compound system and application thereof in glass fiber reinforced engineering plastic |
| CN111171562A (en) * | 2020-02-18 | 2020-05-19 | 江苏博云塑业股份有限公司 | Halogen-free flame-retardant glass fiber reinforced nylon material and preparation method thereof |
| CN112210118A (en) * | 2020-10-12 | 2021-01-12 | 江苏利思德新材料有限公司 | High-heat-resistant high-shear-resistant high-flame-retardant halogen-free flame-retardant compound system and application thereof |
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| WO2019100929A1 (en) * | 2017-11-22 | 2019-05-31 | 江苏利思德新材料有限公司 | Phosphor aluminium compound-based halogen-free flame retardant compound system and application thereof in glass fiber reinforced engineering plastic |
| CN108795039A (en) * | 2018-06-28 | 2018-11-13 | 浙江大学 | The halogen-free flame-retardant system and its application that dialkyl dithio hypophosphites is cooperateed with organic phosphite |
| CN108948430A (en) * | 2018-06-28 | 2018-12-07 | 浙江大学 | The thio hypophosphites of dialkyl group list, the halogen-free flame-retardant system of organic phosphite and nitrogenous compound collaboration and its application |
| CN108795038A (en) * | 2018-06-28 | 2018-11-13 | 浙江大学 | The halogen-free flame-retardant system and its application that the thio hypophosphites of dialkyl group list is cooperateed with inorganic phosphite |
| CN108795038B (en) * | 2018-06-28 | 2020-12-11 | 浙江大学 | Halogen-free flame retardant system with synergistic effect of dialkyl monothio hypophosphite and inorganic phosphite and application thereof |
| CN108948419A (en) * | 2018-08-03 | 2018-12-07 | 张家港市五湖新材料技术开发有限公司 | A kind of preparation method of aluminium phosphorus synergistic fire retardant |
| CN109082116A (en) * | 2018-08-09 | 2018-12-25 | 江苏利思德新材料有限公司 | Thermoplastic polymer or the high-temperature thermal stability method of its compound are improved using alkyl phosphorous acid metal salt |
| CN109181293A (en) * | 2018-08-09 | 2019-01-11 | 浙江大学 | Melamine derivative based flame retardant high-temperature thermal stability method and products thereof and application are improved using inorganic and alkyl phosphorous acid metal salt |
| CN109181293B (en) * | 2018-08-09 | 2021-03-05 | 浙江大学 | Method for improving high-temperature thermal stability of melamine derivative flame retardant by using inorganic and alkyl phosphite metal salt, product and application thereof |
| CN111171562A (en) * | 2020-02-18 | 2020-05-19 | 江苏博云塑业股份有限公司 | Halogen-free flame-retardant glass fiber reinforced nylon material and preparation method thereof |
| CN112210118A (en) * | 2020-10-12 | 2021-01-12 | 江苏利思德新材料有限公司 | High-heat-resistant high-shear-resistant high-flame-retardant halogen-free flame-retardant compound system and application thereof |
| CN112210118B (en) * | 2020-10-12 | 2022-05-17 | 江苏利思德新材料有限公司 | High-heat-resistant high-shear-resistant high-flame-retardant halogen-free flame-retardant compound system and application thereof |
| CN114479443A (en) * | 2022-01-17 | 2022-05-13 | 青岛欧普瑞新材料有限公司 | Halogen-free flame retardant for thermoplastic polymer and preparation method thereof |
| WO2023168790A1 (en) * | 2022-03-10 | 2023-09-14 | 江苏利思德新材料有限公司 | Aluminum diethylphosphinate crystal with low fine powder content, and preparation method therefor and use thereof |
| CN114573868A (en) * | 2022-03-18 | 2022-06-03 | 江苏利思德新材料有限公司 | Aluminum phosphite-alkyl aluminum phosphite composite salt and preparation method and application thereof |
| CN114573868B (en) * | 2022-03-18 | 2023-02-03 | 江苏利思德新材料有限公司 | Aluminum phosphite-alkyl aluminum phosphite composite salt and preparation method and application thereof |
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