CN1202917A - Flame-resistant polyamides - Google Patents

Flame-resistant polyamides Download PDF

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Publication number
CN1202917A
CN1202917A CN96198484A CN96198484A CN1202917A CN 1202917 A CN1202917 A CN 1202917A CN 96198484 A CN96198484 A CN 96198484A CN 96198484 A CN96198484 A CN 96198484A CN 1202917 A CN1202917 A CN 1202917A
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carbon atom
group
polymeric amide
phosphide
alkylidene
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沃尔夫冈·冯根茨科
海因里希·卡皮特扎
迈克尔·施赖尔
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Siemens AG
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Siemens AG
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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
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/303—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups H01B3/38 or H01B3/302
    • H01B3/305—Polyamides or polyesteramides
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/48—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids
    • C08K5/5357—Esters of phosphonic acids cyclic
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K5/5398—Phosphorus bound to sulfur
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyamides (AREA)

Abstract

To produce flame-resistant polyamides, a polyamide, a co-polyamide or polyamide blend is reacted at high temperature with a monoepoxy-functional phosphorous compound in the form of an addition product of a phosphonic or phosphinic acid anhydride with a polyepoxy compound. The proportion of phosphorous compound is 5-35 wt % of the total weight i.e. of the polyamide mixture.

Description

Flame-resistant polyamides
The present invention relates to a kind of method for preparing flame-resistant polyamides.
Synthesizing polyamides (PA) is applied at many industrial circles, and is used widely in daily life.This mainly is because polymeric amide has good processing properties, and can polymkeric substance be cut into certain size according to application requiring.Nearly 90% polymeric amide uses PA6 (poly--ε-Ji Neixianan) and PA66 (polyhexamethylene adipamide) type; Remaining 10% use PA11 (nylon 11), PA12 (poly--ε-laurin lactan), PA610 (polyhexamethylene sebacoyl amine) and PA612 (polyhexamethylene lauramide) and copolyamide.Polyamide product more than 80% is processed to fiber and fabric in the world; Less than 20% is used for industrial circle, especially automobile making, electronic industry, packing business and machine and equipment manufacturing.By strengthening the good mechanical properties that can reach industrial common requirement with fiber or mineral filler.In electronics industry, because polymeric amide has high insulating property, good creep currents intensity and solvent resistance and good thermomechanical property, proved to be particularly suitable for as insulation with switching member, magnetic valve, rail-engaging, cable mounting block, coil stand, connector is connected and housing.
Though polymeric amide from horizontal blanking, then can lose this character behind interpolation filler such as glass fibre or the pigment according to several testing method.For the many application in electronic industry and the automobile making, the polymeric amide that needs resistivity against fire to be strengthened.Its resistivity against fire should provide time enough to rescue people and valuable article when presence of fire.
At present, industrial most use organohalogen compound and red phosphorus are as fireproofing agent.Halogen compounds mainly is chlorinated hydrocarbon or brominated hydrocarbon, they usually with zn cpds or and synergy is arranged but in animal experiment carcinogenic ANTIMONY TRIOXIDE SB 203 99.8 PCT chemical combination.The shortcoming of halogen compounds is to discharge highly corrosive and highly toxic degradation production for example hydrogenchloride and hydrogen bromide when presence of fire, and forms free annexation and dense smoke; In addition, also can reduce the toughness and the creep currents intensity of polymeric amide.Red phosphorus uses with capsule form mostly.Though capsule is arranged, under high processing temperature, still has the danger of phosphorus incendiary.Phosphine and phosphoric acid salt may produce blast when disproportionation, thereby cause the bigger damage of processor.Other shortcoming is with the electrocorrosion extreme difference of red phosphorus fp polyamide material and is dark-coloured.
For fear of the shortcoming relevant with halogen compounds and red phosphorus, people are in the past few years making great efforts the flame-resistant polyamides that exploitation does not contain this fireproofing agent always.Nitrogen compound such as dicyanodiamide (DE-OS3909145), melamine and melamine salt (DE-OS3609341 and DE-OS4141861) and melamine affixture (DE-OS3722118) have been proposed for example to use for this reason.Yet, especially in order to make glass fiber-reinforced material have enough fire lines, to such an extent as to need very high compactedness to influence mechanical property.Further the magnesium hydroxide that proposes (" plastics ", 80 volumes, (1990), 1107-1112 page or leaf) can reduce physical strength equally under required high density; In addition, the decomposition of the water that takes place under processing temperature can form bubble.For the polymeric amide of part aromatize, also the someone proposes to use the poly phosphate (DE-OS3613490) of high density.But, also unsatisfactory in the resistivity against fire that high glass fibre compactedness is issued to; Can have a strong impact on the mechanical property of polymeric amide in addition.
In addition, the somebody proposes, and enters in the presence of the compound of polymer chain to carry out synthesizing of polymeric amide when polymerization.For example advise the ε-Ji Neixianan polymerization is used the N-phosphoric acid salt (referring to " Journal of Applied Polymer Science ", Vol.47 (1993), 1185-1192 page or leaf) of N-phosphoric acid salt and ε-Ji Neixianan.In addition, also the someone proposes for example by making 3,3 '-diamino-diphenyl-phosphine oxide and 1,3-phenylene isophthaloyl amine reacts to synthesize phosphorous multipolymer, and use this multipolymer as fireproofing agent (referring to " Journal of Polymer Science, Part A, Polymer Chemistry ", Vol.30 (1992), 2521-2529).From required in this case high expense, the flame retardant resistance that is reached can not satisfy the requirement of industry.
Task of the present invention is, propose a kind of enforceable method simple, with low cost and prepare the polymeric amide that can satisfy industrial resistivity against fire, this polymeric amide is halogen contained compound and red phosphorus not, but still can successfully process, can dye light color, satisfy all requirements of electricity, chemistry, machinery and thermal property, needing especially to be suitable for the electronic industry and the electronics of mass filler.
Technical scheme of the present invention is, make a kind of polymeric amide, a kind of copolyamide or a kind of polyamide compound at high temperature with the phosphide reaction of the monocycle oxygen functional group that following structure is arranged,
Figure A9619848400051
Figure A9619848400061
In the formula: n=one 1 to 6 integer,
The bivalent hydrocarbon radical of A=one 1 to 4 carbon atom,
Z=O or S,
R 1The alkyl or phenyl of=1 to 4 carbon atom,
R 2To R 7The alkyl of=hydrogen or 1 to 4 carbon atom, R 3And R 4Or R 5And R 6Can be total to
Be all the alkylidene bridge of 1 to 4 carbon atom, R 2And R 7Can be jointly
An alkylidene bridge in the carbocyclic ring of maximum 8 carbon atoms,
R 8The alkylidene group of=one singly-bound, 1 to 4 carbon atom, 1 to 4 carbon atom
The alkylidene group oxyalkylene or the arylidene of alkylidene group oxygen, 2 to 4 carbon atoms,
R 9The alkylidene group of=one singly-bound, 1 to 4 carbon atom, 1 to 4 carbon atom
The alkylidene group oxyalkylene of oxyalkylene, 2 to 4 carbon atoms, one have two
The substituting group of phenol A group or an isocyanuric acid foundation group, R 8And R 9Can
Being one-CH jointly 2-O-CO-group,
Wherein the content of phosphide is 5 to 35% (quality), is benchmark with total quality, that is to say the quality of the mixture (polyamide compound) of polymeric amide and phosphide and additive in case of necessity.
Find unexpectedly, as above carry out, phosphide is fixed on the polymer chain with chemical mode according to the present invention.Therefore, can obtain the polymeric amide of phosphorus modification by a kind of simple method, the not halogen-containing and red phosphorus of this polymeric amide has enough flame retardant resistances, and can satisfy all industrial requirements.True also further proof, the flame retardant resistance that is reached are only relevant with the quantity of fixed phosphorus on the polymer chain.
At high temperature, the method for the present invention of also promptly carrying out under the temperature of 〉=150 ℃ (upper limits :≤300 ℃) usually can for example be carried out in kneader, roll mixing machine and the extrusion machine at known heatable mixing equipment.The premixture of both can be earlier in for example drum tumbler or fluidisation mixing machine, making polymeric amide and phosphide, also can directly be metered into phosphide in the polyamide melt, it is distributed also and polyamide reaction, that is to say to be fixed on the polymer chain.In order when adding phosphide, to avoid vaporization losses, proved that favourable way is to use the phosphide of molar weight 〉=190.Simultaneously, can add other additive, for example filler, especially glass fibre, and dyestuff, protective agent, processing aid or the like are distributed in the polymeric amide it; Also can use filler mixture.But the sneaking into also can give of additive carried out earlier or carried out in the mixing step of back.
In the method for the invention, can preferably add other not halogen-containing fireproofing agent to polyamide compound.Such fireproofing agent is preferably melamine cyanurate, melamine phosphate and magnesium hydroxide.
The phosphide that the present invention uses is known (referring to DE-OS 4308185).The preparation of these phosphides is preferably undertaken by phosphoric anhydride or phosphonic acid anhydride are added on the polyepoxide with 2 to 7 epoxy group(ing).The example of operable polyepoxide is a diepoxybutane, two (2,3-oxirane ring amyl group)-ether, two cyclohexadiene-dioxide, the vinyl cyclohexene dioxide, epoxidised polyhutadiene, epoxidised polyisoprene, diglycidyl ether, the ethylene glycol bisthioglycolate glycidyl ether, butanediol diglycidyl ether, 1,2,3-triglycidyl group propane is (referring to table 1, IX number), the TriMethylolPropane(TMP) diglycidyl ether, tetramethylolmethane four glycidyl group ether is (referring to table 1, X number), polyene propyl group glycidyl ether, dihydroxyphenyl propane diglycidyl ether (referring to table 1, VI number), divinylbenzene dioxide, epoxidised phenol or cresols phenolic varnish, the three-glycidyl based isocyanate, epoxidised glycidyl acrylate, epoxidised poly epihydric alcohol base acrylate, epoxidised glycidyl methacrylate and epoxidised shrink polyglyceryl methacrylic ester.
The amount of regulating the required phosphide of polymeric amide resistivity against fire is relevant with its chemical structure and additive.For example, polymeric amide PA6 and PA66 lack than polymeric amide PA11 and the required phosphide of PA12.On the other hand, the polyamide compound phosphide concentration height more required that contains high level filler such as glass fibre than the mixture that does not contain filler.Therefore, required phosphorus content is 1 to 5% (quality), is benchmark with the polyamide compound.Because the resistivity against fire of polymeric amide is only relevant with the phosphorus concentration in the polymeric matrix, so can use the phosphide of different amounts.With the phosphorus content of phosphide, be benchmark with the polyamide compound as required, its necessary share is 5 to 35% (quality).
Method of the present invention especially has following advantage:
-can one mix or extrusion process in very simply and carry out the modification of polymkeric substance inexpensively, in any case homogenizing polymeric amide or will carry out when mixing during just as preparation for many industrial purposes;
The processing characteristics of-polymeric amide and various character are not subjected to the influence of phosphorus modification basically;
-can successfully make polymeric amide be light color;
-polymeric amide does not contain volatile constituent, so can not injure when using in electronic industry and electronics or passivation electrically contacts;
-polymeric amide does not discharge corrosive component;
-polymeric amide can recycle.
Flame-resistant polyamides according to method manufacturing of the present invention can advantageously be used as insulation, structure and case material in electronic industry and electronics.Other use field it is also conceivable that automobile making, textile industry, packaging industry and machinery and device fabrication.
Further specify the present invention by means of embodiment below.
In order to make polyamide mold plastic, use following component:
Component A: relative viscosity η RelBe 2.9 (according to ISO307 as at 96% H 2SO 4In the measured viscosity of 0.5% solution) polyamide 6;
B component: relative viscosity η RelIt is 2.7 polyamide 66;
Component C: mean diameter is the glass fibre of 10 μ m.
Listed the phosphide I to X that uses in the table 1; The preparation of these compounds is carried out in the described mode of DE-OS4308185.
The preparation (embodiment 1 to 13) of mixture or corresponding moulding compound
Mixture prepares the amount of required component A to C and phosphide I to X and lists in table 2.Preparation is during mixture, component A or B measured under part (MT) in 240 to 260 ℃ accordingly plastify in a Brabender biaxial kneader, adds the phosphide I to X of respective amount part then, makes it lubricant effect not occur.At least mediate 5 minutes after adding phosphide,, and be fixed on the polymeric matrix with chemical mode so that make phosphide well distributed.Add component C again after adding phosphide in case of necessity, after this mediated at least 5 minutes again.After kneading process finishes, from kneader, take out mixture and cooling.Grind the refrigerative melt then, and splash is to model.On model, measure resistivity against fire, measure modulus of elasticity, measure impelling strength according to DIN 53453 according to DIN 53457 according to UL 94 V (the sample rod that 1.6mm is thick).What obtain the results are shown in the table 2.
The preparation (embodiment 14) of mixture or corresponding moulding compound
(ZSK 32 at a double-shafted extruder to make the polyamide 6 (component A) of the amount part shown in the table 2, Werner and Pfleiderer company) in the down plasticizing of 250 ℃ of temperature of charge, be metered into the phosphide II of described amount part then by a hole on the extruder barrel, and sneak in the plastifying polymkeric substance.Melt is expressed in the water-bath, and pulverizing, dry also splash are to model.The results are shown in the table 2.
Table 1
The phosphorus compound of following formula
Figure A9619848400091
The composition of table 2 mixture and the test result of moulding compound
Embodiment 123456789 10 11 12 13 14
Composition A (MT) 85 82 57-59 80 75 50 70---60 82
Composition B (MT)---57-----55 55 60--
Composition C (MT)--25 25 25--25-25 25 25 25-
Phosphorus compound I (MT) 15-------------
Phosphorus compound II (MT)-18 18 18---------18
Phosphorus compound III (MT)----16---------
Phosphorus compound IV (MT)-----20--------
Phosphorus compound V (MT)------25 25------
Phosphorus compound VI (MT)--------30-----
Phosphorus compound VII (MT)---------20----
Phosphorus compound VIII (MT)----------20---
Phosphorus compound IX (MT)-----------15--
Phosphorus compound X (MT)------------15-
Phosphorus content (%) 2,42 2,46 2,46 2,46 2,38 2,22 2,52,52,04 2,24 2,52,27 2,39 2,46
Test result: UL94 V/l, 6mm V-O V-O V-O V-O V-O V-O V-O V-1 V-1 V-O V-O V-O V-O V-O
Impelling strength (kJ/m 2) 40 40 48 48 40 41 40 47 38 48 47 48 47 40
Tear elongation (%) 10 94 3.5 4984843,53,57 10 modulus of elasticity (N/mm 2) 8,500 8,600 8,500 10,000 8,500 8,200 8,000 8,500 8,200 11,000 10,000 10,000 8,600 8500

Claims (6)

1. the preparation method of flame-resistant polyamides is characterized in that, make a kind of polymeric amide, a kind of copolyamide or a kind of polyamide compound at high temperature with the reaction of the phosphide of the monocycle oxygen functional group that following structure is arranged,
Figure A9619848400021
N in the formula=one 1 to 6 integer,
The bivalent hydrocarbon radical of A=one 1 to 4 carbon atom,
Z=O or S,
R 1The alkyl or phenyl of=1 to 4 carbon atom,
R 2To R 7The alkyl of=hydrogen or 1 to 4 carbon atom, R 3And R 4Or R 5And R 6Can be total to
Be all the alkylidene bridge of 1 to 4 carbon atom, R 2And R 7Can be jointly
An alkylidene bridge in the carbocyclic ring of maximum 8 carbon atoms,
R 8The alkylidene group of=one singly-bound, 1 to 4 carbon atom, the Asia of 1 to 4 carbon atom
The alkylidene group oxyalkylene or the arylidene of alkyl oxygen, 2 to 4 carbon atoms,
R 9The alkylidene group of=one singly-bound, 1 to 4 carbon atom, the oxygen of 1 to 4 carbon atom
The alkylidene group oxyalkylene of alkylidene group, 2 to 4 carbon atoms, one have bis-phenol
The substituting group of A group or an isocyanuric acid foundation group, R 8And R 9Can be total to
Be all one-CH 2-O-CO-group,
Wherein the content of phosphide is 5 to 35% (quality), is benchmark with total quality.
2. in accordance with the method for claim 1, it is characterized in that, with a kind of additive, in especially a kind of filler absorption polymeric amide.
3. in accordance with the method for claim 2, it is characterized in that, use glass fibre as filler.
4. according to described method one of in the claim 1 to 3, it is characterized in that, in polymeric amide, add a kind of not halogen-containing fireproofing agent.
5. in accordance with the method for claim 4, it is characterized in that, use melamine cyanurate, melamine phosphate or magnesium hydroxide as fireproofing agent.
6. the flame-resistant polyamides that obtains of the one or more of described method in the claim 1 to 5 is as the application of insulating material, structured material and case material or the application in textile industry.
CN96198484A 1995-11-24 1996-11-11 Flame-resistant polyamides Pending CN1202917A (en)

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DE19543890A DE19543890A1 (en) 1995-11-24 1995-11-24 Flame retardant polyamides
DE19543890.6 1995-11-24

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DE (1) DE19543890A1 (en)
WO (1) WO1997019119A2 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109898330A (en) * 2018-10-18 2019-06-18 天津工业大学 A kind of preparation method of the aqueous sizing agent of modified polycaprolactam carbon fiber
CN115175957A (en) * 2020-02-26 2022-10-11 原子能和替代能源委员会 Chemical modification process for polymer components

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3107528B1 (en) * 2020-02-26 2022-02-04 Commissariat Energie Atomique PROCESS FOR CHEMICAL MODIFICATION OF A POLYMERIC PART WITH A VIEW TO GIVEN IT FIRE-RETARDANT PROPERTIES OR TO IMPROVE THESE PROPERTIES INVOLVING A COVALENT REACTION WITH AT LEAST ONE COMPOUND CARRIER OF AN ISOCYANATE GROUP
FR3135460A1 (en) * 2022-05-12 2023-11-17 Commissariat A L'energie Atomique Et Aux Energies Alternatives METHOD FOR CHEMICAL MODIFICATION OF A POLYMERIC PART IN ORDER TO PROVIDE IT WITH FIRE-RETARDANT PROPERTIES OR IMPROVE THEM

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5756638A (en) * 1993-03-15 1998-05-26 Hoechst Ag Phosphorus-modified epoxy resins, process for the preparation thereof and use thereof
DE4308185A1 (en) * 1993-03-15 1994-09-22 Siemens Ag Phosphorus-modified epoxy resins, process for their preparation, and their use

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109898330A (en) * 2018-10-18 2019-06-18 天津工业大学 A kind of preparation method of the aqueous sizing agent of modified polycaprolactam carbon fiber
CN115175957A (en) * 2020-02-26 2022-10-11 原子能和替代能源委员会 Chemical modification process for polymer components

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WO1997019119A2 (en) 1997-05-29
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JP2000500517A (en) 2000-01-18
KR19990071522A (en) 1999-09-27

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