CN102382253A - Organic complex and preparation method thereof as well as flame-retarding material and preparation method thereof - Google Patents
Organic complex and preparation method thereof as well as flame-retarding material and preparation method thereof Download PDFInfo
- Publication number
- CN102382253A CN102382253A CN2010102748428A CN201010274842A CN102382253A CN 102382253 A CN102382253 A CN 102382253A CN 2010102748428 A CN2010102748428 A CN 2010102748428A CN 201010274842 A CN201010274842 A CN 201010274842A CN 102382253 A CN102382253 A CN 102382253A
- Authority
- CN
- China
- Prior art keywords
- fire retardant
- content
- preparation
- organic complex
- matrix resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92561—Time, e.g. start, termination, duration or interruption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92828—Raw material handling or dosing, e.g. active hopper or feeding device
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92885—Screw or gear
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92904—Die; Nozzle zone
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention provides an organic complex and a preparation method thereof as well as a flame-retarding material and a preparation method thereof. The organic complex disclosed by the invention and a hydroxide flame retardant commonly form a flame-retarding system; in a matrix taking polyolefine as main body resin, the flame-retarding system plays a favorable flame-retarding action under the condition of small addition amount of the hydroxide flame retardant; and in addition, a flame-retarding material has excellent mechanical performance.
Description
Technical field
The present invention relates to a kind of organic complex and preparation method thereof and a kind of fire retardant material and preparation method thereof.
Background technology
Along with industrial expansion; Macromolecular material is more and more many is applied to all respects in each department of national economy and the people's lives; Particularly polyolefine has characteristics such as specific density is little, chemical proofing, water-tolerant, excellent mechanical intensity, electrical insulating property because of it.Can be used for film, tubing, sheet material, various moulded products, electric wire etc.Have been widely used at aspects such as agricultural, packing, electronics, electric, automobile, machinery, daily use Sundry goodss.
But most of macromolecular materials such as polyolefine are all inflammable, had a strong impact on the security of its use, and the flame retardant properties that therefore improves macromolecular material is to need the problem of solution badly.In the prior art, method commonly used is when the above-mentioned macromolecular material of preparation, in raw material, adds fire retardant.Fire retardant well known in the art comprises halogen containing flame-retardant, expansion type flame retardant and oxyhydroxide fire retardant.Wherein, what flame retardant effect was best is halogen containing flame-retardant, but the macromolecular material that has halogen containing flame-retardant in the material can produce a large amount of toxic products when burning, do not meet environmental requirement.Nowadays, halogen-free flame retardants has become the industry development trend.The flame retardant effect of expansion type flame retardant and oxyhydroxide fire retardant is also not obvious, need under the situation of big addition, just can play effect.Yet the expansion type flame retardant of heavy addition or oxyhydroxide fire retardant can seriously reduce the mechanical property of material again, hinder being widely used of material.
Summary of the invention
For overcome halogen-free flame retardants of the prior art need be under the big situation of addition the problem of competence exertion flame retardant effect; The invention provides a kind of organic complex; Through this organic complex and the acting in conjunction of oxyhydroxide fire retardant; Can under the prerequisite that guarantees flame retardant effect, reduce the addition of oxyhydroxide fire retardant greatly, make the mechanical property of material unaffected.
Organic complex disclosed by the invention has the structure shown in the formula 1,
Formula 1:
Wherein, R1 is selected from a kind of in two (the two amidine propane) dihydrochlorides of Diisopropyl azodicarboxylate, ABVN, azo, the azo two isopropylformic acid dimethoxy nitriles; R2 is selected from the alkyl or alkenyl that carbonatoms is 1-4, and R3 is selected from a kind of in alkyl that hydrogen, carbonatoms are 1-4, the thiazolinyl that carbonatoms is 1-4; M is the ion of complexing metal, and said complexing metal is selected from a kind of in IVB family or the VIIB family metal; N is selected from the integer of 1-100.
Simultaneously, the invention also discloses the preparation method of above-mentioned organic complex, comprising:
A, monomer, linking agent and initiator are mixed, and under heating condition, react; Wherein, Said monomer is N-(4-aminomethyl phenyl) acrylamide monomer and/or N-(p-hydroxy phenyl) acrylamide monomer; Said linking agent is selected from 4; 4 '-in the amino disulfoxide of two (acrylic amide) sulfobenzide, Trimethylsulfoxonium Iodide, DMSO 99.8MIN., 2-, tetramethylene sulfone one or more, said initiator is selected from one or more in Diisopropyl azodicarboxylate, ABVN, two (the two amidine propane) dihydrochlorides of azo, the azo two isopropylformic acid dimethoxy nitriles;
B, under heating condition, the salts solution of complexing metal is splashed in the above-mentioned product, and stirs, said complexing metal is selected from a kind of in IVB family or the VIIB family metal;
C, with the product of step b through filtering, washing, and filtering once more and get final product.
In addition, the invention also discloses a kind of fire retardant material, comprise matrix resin, fire retardant and organic complex; Wherein, said matrix resin is a polyolefine, and said fire retardant is the oxyhydroxide fire retardant; Organic complex is above-mentioned organic complex, the product that perhaps obtains through method for preparing.
This fire retardant material can join through the raw mix that will contain said matrix resin, fire retardant and organic complex in the forcing machine; The control extruder temperature is 160-220 ℃; Head temperature is 200-220 ℃; Screw speed is 50-350rpm, and rate of feeding is that 10-50rpm extrudes, and obtains through granulation, injection moulding then.
The contriver finds; Through in the material of oxyhydroxide as fire retardant; Add organic complex disclosed by the invention; Can guarantee Flame Retardancy can prerequisite under, reduce the usage quantity of oxyhydroxide significantly, thereby avoid the mechanical property of the fire retardant material that the heavy addition of oxyhydroxide causes seriously to descend.
Embodiment
Clearer for technical problem, technical scheme and beneficial effect that the present invention is solved, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
Organic complex disclosed by the invention has the structure shown in the formula 1, and wherein, R1 is selected from a kind of in two (the two amidine propane) dihydrochlorides of Diisopropyl azodicarboxylate, ABVN, azo, the azo two isopropylformic acid dimethoxy nitriles; R2 is selected from the alkyl or alkenyl that carbonatoms is 1-4, and R3 is selected from a kind of in alkyl that hydrogen, carbonatoms are 1-4, the thiazolinyl that carbonatoms is 1-4; M is the ion of complexing metal, and said complexing metal is selected from a kind of in IVB family or the VIIB family metal; N is selected from the integer of 1-100.
Formula 1:
Under the preferable case, said R1 is Diisopropyl azodicarboxylate (DMF); R2 is selected from the alkyl or alkenyl that carbonatoms is 2-3, and R3 is selected from hydrogen or carbonatoms is the alkyl of 2-3; M is selected from a kind of in mn ion, iron ion, cobalt ion, nickel ion, zine ion, the cupric ion; N is selected from the integer of 10-90.
Simultaneously, the invention also discloses the preparation method of above-mentioned organic complex, comprise the steps:
A, monomer, linking agent and initiator are mixed, and under heating condition, react; Wherein, Said monomer is N-(4-aminomethyl phenyl) acrylamide monomer and/or N-(p-hydroxy phenyl) acrylamide monomer; Said linking agent is selected from 4; 4 '-in the amino disulfoxide of two (acrylic amide) sulfobenzide, Trimethylsulfoxonium Iodide, DMSO 99.8MIN., 2-, tetramethylene sulfone one or more, said initiator is selected from one or more in Diisopropyl azodicarboxylate, ABVN, two (the two amidine propane) dihydrochlorides of azo, the azo two isopropylformic acid dimethoxy nitriles;
B, under heating condition, the salts solution of complexing metal is splashed in the above-mentioned product, and stirs, said complexing metal is selected from a kind of in IVB family or the VIIB family metal;
C, with the product of step b through filter, washing, and filter once more after obtain organic complex.
Under the preferable case, the temperature that heats among the step a is 40-80 ℃, and the reaction times is 5-40min; The temperature that heats among the step b is 40-80 ℃.
Said monomer is N-(4-aminomethyl phenyl) acrylamide monomer, said linking agent is 4,4 '-two (acrylic amide) sulfobenzide, said initiator is 4,4 '-two (acrylic amide) sulfobenzide.
Wherein, in above-mentioned steps a, the mol ratio of said monomer and linking agent, initiator is 0.05-1: 0.01-1: 1.That is, when monomer is N-(4-aminomethyl phenyl) acrylamide monomer, said linking agent is 4; 4 '-two (acrylic amide) sulfobenzide; Said initiator is 4,4 '-during two (acrylic amide) sulfobenzide, N-(4-aminomethyl phenyl) acrylamide monomer and 4; 4 '-mol ratio of two (acrylic amide) sulfobenzide, Diisopropyl azodicarboxylate is 0.05-1: 0.01-1: 1, be preferably 0.5-1: 0.05-1: 1.
In step b, the salt of said complexing metal is soluble salt a kind of in manganese, iron, cobalt, nickel, zinc, the copper.For example, the vitriol of manganese, iron, cobalt, nickel, zinc, copper, nitrate salt or muriate, perhaps the solubility acetate of above-mentioned metal, for example manganese acetate.Above-mentioned soluble salt only needs water-soluble the getting final product of ability, to not too big requirement of negatively charged ion.
In the molar content of complexing metal, the salt of complexing metal and monomeric mol ratio are 0.01-1: 1.Equally, when monomer was N-(4-aminomethyl phenyl) acrylamide monomer, in the molar content of complexing metal, the mol ratio of the salt of complexing metal and N-(4-aminomethyl phenyl) acrylamide monomer was 0.01-1: 1, be preferably 0.5-1: 1.
The various materials that adopted among abovementioned steps a and the step b, as N-(4-aminomethyl phenyl) acrylamide monomer, 4,4 '-two (acrylic amide) sulfobenzides and Diisopropyl azodicarboxylate be the known raw material of chemical field, can directly be commercially available.
According to the present invention, in the salts solution of said complexing metal, the concentration of the salt of complexing metal is 0.01-1mol/l, is preferably 0.05-1mol/l.
After the product that step b is prepared filters out, through washing, can obtain organic complex disclosed by the invention after filtering once more.Because the uncertainty of organic synthesis, preparation method disclosed by the invention are not meant that the product of this method is hundred-percent and are the organic complex of aforementioned structure, and this method is merely the method that can prepare the said structure organic complex.
On the basis of above organic complex; The invention also discloses a kind of fire retardant material, comprise matrix resin, fire retardant and organic complex, wherein; Said matrix resin is a polyolefine; Said fire retardant is the oxyhydroxide fire retardant, and said organic complex is above-mentioned organic complex, we can say that perhaps said organic complex is the product that method for preparing obtains.
According to the present invention; Through being in the material of matrix with the polyolefine; The oxyhydroxide that adopts environmental protection is as fire retardant; And combine the acting in conjunction of the product that above-mentioned organic complex or method for preparing obtain, can make the oxyhydroxide fire retardant under the situation of seldom addition, can play good flame-retardant effect, thereby guarantee the mechanical property of material.Though above-mentioned preparing method's product is not the hundred-percent organic complex of aforementioned structure that is, in the present invention, adopt this preparing method's product (possibly be mixture) can realize its purpose.
Said polyolefine is a various polyolefine commonly known in the art, for example, and Vilaterm, Vestolen PP 7052 or ethylene propylene copolymer or the like; Under the preferable case; Said polyolefine adopts Vestolen PP 7052, and further, this Vestolen PP 7052 specifically can be COPP and/or HOPP.As fire retardant material, in use general requirement has favorable rigidity and toughness.So under the preferable case, the resin that is adopted in the fire retardant material disclosed by the invention contains COPP and HOPP simultaneously.Above-mentioned COPP is preferably second third COPP.
Aforesaid oxyhydroxide fire retardant is a various oxyhydroxide well known in the art, for example: one or more in white lake, Marinco H, the layered double-hydroxide.The preferred white lake that adopts.
In above-mentioned fire retardant material, various components contents do not have too limitations, can be for known in those skilled in the art; Under the preferable case, be benchmark with the content of said matrix resin, the content of said fire retardant is 5-60wt%; The content of said organic complex is 2-25wt%; The content that further is preferably with said matrix resin is benchmark, and the content of said fire retardant is 10-50wt%, and the content of said organic complex is 5-20wt%.
For further improving the mechanical property of material, can also contain this area various auxiliary agents commonly used in the said fire retardant material, for example one or more in oxidation inhibitor, compatilizer, the coupling agent; Content with said matrix resin is benchmark, and the content of said oxidation inhibitor is 0-1wt%, and the content of said compatilizer is 0-5wt%; The content of said coupling agent is 0-5wt%; The content of said oxidation inhibitor, compatilizer, coupling agent is not 0 simultaneously, and the content that is preferably with said matrix resin is benchmark, and the content of said oxidation inhibitor is 0.05-0.5wt%; The content of said compatilizer is 0.05-4wt%, and the content of said coupling agent is 0.05-4wt%.
Concrete; Above-mentioned oxidation inhibitor, compatilizer, coupling agent are the frequent use in this area; For example; Said oxidation inhibitor can be Hinered phenols, nitrogen heterocyclic ring Polyphenols, phosphorous acid ester, monothioester class, and the mixture of hindered phenol and phosphorous acid ester, monothioester, is preferably hindered phenol and phosphorous acid ester according to 1: 1 mixture of part by weight; Composite between hindered phenol and the phosphite antioxidant, not only can improve material property, strengthen antioxidant effect, also can reduce cost.The all available mistake of above-mentioned various oxidation inhibitor is commercially available, like 1010 and 168 of vapour Bagong department production.
Said coupling agent is this area various coupling agents commonly used, for example silane coupling agent and/or titanate coupling agent.
The compatilizer that adopts among the present invention can be various compatilizers commonly used in the prior art; For example can be the grafts of new LDPE (film grade), for example grafted low density polyethylene maleic anhydride (LDPE-g-MAH), grafted low density polyethylene diallyl bisphenol ether (LDPE-g-DBAE), allyl group Bisphenol A Ether grafting new LDPE (film grade).Can also be SEBS or the high anti-Ying of SEEPS grafting oxazoline group, the grafts of polypropylene grafted maleic anhydride or vinylformic acid, TEB 3K, polypropylene grafted toluene propylene glycidyl ether (PP-g-GMA).Above-mentioned compatilizer can be commercially available, like the maleic anhydride inoculated polypropylene (MAH-g-PP) of the inferior plastic cement of Changzhou light ltd production.
As a kind of preferred scheme disclosed by the invention, said matrix resin is selected Vestolen PP 7052 for use; And contain oxidation inhibitor, compatilizer and coupling agent in the said fire retardant material simultaneously, said oxyhydroxide fire retardant is selected white lake for use; Content with said matrix resin is benchmark, and the content of said oxidation inhibitor is 0.1-0.5wt%, and the content of said compatilizer is 0.5-4wt%, and the content of said coupling agent is 0.5-4wt%.
In addition, the invention also discloses the preparation method of above-mentioned fire retardant material, this preparation method can adopt method well known in the art; For example the preparation method of this fire retardant material comprises: the raw mix that will contain said matrix resin, fire retardant and organic complex joins in the forcing machine; The control extruder temperature is 160-220 ℃, and head temperature is 200-220 ℃, and screw speed is 50-350rpm; Rate of feeding is that 10-50rpm extrudes, and obtains fire retardant material through granulation, injection moulding then.Preferably when melt extruding, set and respectively distinguish temperature and be: 1 district 160-170 ℃, 2 district 170-180 ℃, 3 district 180-190 ℃, 4 district 160-180 ℃; 5 district 160-180 ℃, 6 district 170-190 ℃, 7 district 170-190 ℃; 8 district 170-190 ℃, 9 district 180-200 ℃, head 190-210 ℃.General twin screw extruder is provided with a plurality of districts of pushing, and by as far as closely being respectively 1-10 district, 1 district leaves extrusion farthest from extrusion, and it is nearest that 10 districts leave extrusion.Can be provided with opening for feed in the district pushing, raw mix is sent in the forcing machine through different opening for feeds, preferably, raw mix of the present invention is sent into the forcing machine from the opening for feed in 1 district.
Under the preferable case; Can be before said raw mix joins in the forcing machine; Also comprise earlier said matrix resin, fire retardant and organic complex are mixed 5-20min down at 40-120 ℃, the raw material that mixes performance to the raising material in extrusion is more favourable.
In the time of need adding auxiliary agent such as oxidation inhibitor, compatilizer, coupling agent during fire retardant material when preparation, can oxidation inhibitor, compatilizer, coupling agent together be mixed with matrix resin, fire retardant and organic complex, extrude then, the granulation injection moulding obtains fire retardant material.Wherein, be benchmark with the content of said matrix resin, the content of said oxidation inhibitor is 0-1wt%, and the content of said compatilizer is 0-5wt%, and the content of said coupling agent is 0-5wt%, and the content of said oxidation inhibitor, compatilizer, coupling agent is not 0 simultaneously.
The injection moulding process that adopts during above-mentioned preparation fire retardant material also is a method well known in the art, for example adopts injection moulding machine under 190-220 ℃, to carry out injection moulding and gets final product.
The fire retardant material that obtains through method for preparing has good flame retardancy and mechanical property, and environmental protection.
Through embodiment the present invention is further described below.
Embodiment 1
Present embodiment is used to explain organic complex disclosed by the invention and preparation method thereof.
With N-(4-aminomethyl phenyl) acrylamide monomer, 4,4 '-two (acrylic amide) sulfobenzides and Diisopropyl azodicarboxylate mix, and in 40 ℃ of reaction 40min down.Wherein, N-(4-aminomethyl phenyl) acrylamide monomer, 4,4 '-mol ratio of two (acrylic amide) sulfobenzides and Diisopropyl azodicarboxylate is 1: 1: 1.
Then under 40 ℃; (concentration is 1mol/l with 1 liter of manganese acetate solution; The mol ratio of manganese acetate and N-(4-aminomethyl phenyl) acrylamide monomer is 1: 1) splash in the above-mentioned product, stir 40min, obtain organic complex A1 after filtering then, wash, also filtering once more.
Embodiment 2
Present embodiment is used to explain organic complex disclosed by the invention and preparation method thereof.
N-(p-hydroxy phenyl) acrylamide monomer, Trimethylsulfoxonium Iodide and azo two isopropylformic acid dimethoxy nitriles are mixed, and react 5min down in 80 ℃.Wherein the mol ratio of N-(p-hydroxy phenyl) acrylamide monomer, Trimethylsulfoxonium Iodide and azo two isopropylformic acid dimethoxy nitriles is 0.5: 0.05: 1.
Then under 80 ℃; (concentration is 0.05mol/l with 2 liters of zinc acetate solutions; The mol ratio of zinc acetate and N-(4-aminomethyl phenyl) acrylamide monomer is 0.1: 1) splash in the above-mentioned product, stir 5min, obtain organic complex A2 after filtering then, wash, also filtering once more.
Embodiment 3
Present embodiment is used to explain organic complex disclosed by the invention and preparation method thereof.
With N-(4-aminomethyl phenyl) acrylamide monomer, 4,4 '-two (acrylic amide) sulfobenzides and Diisopropyl azodicarboxylate mix, and in 50 ℃ of reaction 20min down.Wherein, N-(4-aminomethyl phenyl) acrylamide monomer, 4,4 '-mol ratio of two (acrylic amide) sulfobenzides and Diisopropyl azodicarboxylate is 0.8: 0.5: 1.
Then under 50 ℃; (concentration is 1mol/l with 0.5 liter of manganese acetate solution; The mol ratio of manganese acetate and N-(4-aminomethyl phenyl) acrylamide monomer is 0.5: 1) splash in the above-mentioned product, stir 20min, obtain organic complex A3 after filtering then, wash, also filtering once more.
Embodiment 4
Present embodiment is used to explain fire retardant material disclosed by the invention and preparation method thereof.
100 weight account polyethylenes, 5 weight part Marinco Hs, 20 weight part A1,0.4 weight part hindered phenol, the polypropylene grafted toluene propylene of 2 weight parts glycidyl ether are joined in the high-speed mixer (the SHR-5A high-speed mixer that the mechanical ltd of the grand base in Zhangjagang City produces) to descend to mix 5min at 80 ℃, obtain raw mix.
The above-mentioned raw materials mixture is dropped into forcing machine, and control feeding rotating speed is 50 rev/mins, and screw speed is 270 rev/mins, and setting extruder temperature is 160 ℃ in 1 district; 170 ℃ in 2 districts, 180 ℃ in 3 districts, 180 ℃ in 4 districts, 180 ℃ in 5 districts; 185 ℃ in 6 districts, 190 ℃ in 7 districts, 185 ℃ in 8 districts, 200 ℃ in 9 districts; Head temperature is set at 205 ℃, melt extrudes, and will extrude the product granulation and be placed in the injection moulding machine, obtains sample S1 through injection moulding.
Embodiment 5
Present embodiment is used to explain fire retardant material disclosed by the invention and preparation method thereof.
100 weight part Vestolen PP 7052,60 weight part white lakes, 5 weight part A2,0.4 weight part hindered phenol, 2 weight part silane coupling agents, the polypropylene grafted toluene propylene of 2 weight parts glycidyl ether are joined in the high-speed mixer (the SHR-5A high-speed mixer that the mechanical ltd of the grand base in Zhangjagang City produces) to descend to mix 15min at 40 ℃, obtain raw mix.
The above-mentioned raw materials mixture is dropped into forcing machine, and control feeding rotating speed is 30 rev/mins, and screw speed is 270 rev/mins, and setting extruder temperature is 170 ℃ in 1 district; 180 ℃ in 2 districts, 190 ℃ in 3 districts, 180 ℃ in 4 districts, 170 ℃ in 5 districts; 180 ℃ in 6 districts, 190 ℃ in 7 districts, 185 ℃ in 8 districts, 200 ℃ in 9 districts; Head temperature is set at 205 ℃, melt extrudes, and will extrude the product granulation and be placed in the injection moulding machine, obtains sample S2 through injection moulding.
Embodiment 6
Present embodiment is used to explain fire retardant material disclosed by the invention and preparation method thereof.
100 weight part Vestolen PP 7052,30 weight part white lakes, 15 weight part A3,0.4 weight part hindered phenol, 2 weight part silane coupling agents, the polypropylene grafted toluene propylene of 2 weight parts glycidyl ether are joined in the high-speed mixer (the SHR-5A high-speed mixer that the mechanical ltd of the grand base in Zhangjagang City produces) to descend to mix 10min at 50 ℃, obtain raw mix.
The above-mentioned raw materials mixture is dropped into forcing machine, and control feeding rotating speed is 50 rev/mins, and screw speed is 270 rev/mins, and setting extruder temperature is 170 ℃ in 1 district; 180 ℃ in 2 districts, 190 ℃ in 3 districts, 180 ℃ in 4 districts, 170 ℃ in 5 districts; 180 ℃ in 6 districts, 190 ℃ in 7 districts, 185 ℃ in 8 districts, 200 ℃ in 9 districts; Head temperature is set at 205 ℃, melt extrudes, and will extrude the product granulation and be placed in the injection moulding machine, obtains sample S3 through injection moulding.
Embodiment 7
Present embodiment is used to explain fire retardant material disclosed by the invention and preparation method thereof.
100 weight part Vestolen PP 7052,40 weight part white lakes, 10 weight part A3,0.4 weight part hindered phenol, 2 weight part silane coupling agents, the polypropylene grafted toluene propylene of 2 weight parts glycidyl ether are joined in the high-speed mixer (the SHR-5A high-speed mixer that the mechanical ltd of the grand base in Zhangjagang City produces) to descend to mix 10min at 50 ℃, obtain raw mix.
The above-mentioned raw materials mixture is dropped into forcing machine, and control feeding rotating speed is 50 rev/mins, and screw speed is 270 rev/mins, and setting extruder temperature is 170 ℃ in 1 district; 180 ℃ in 2 districts, 190 ℃ in 3 districts, 180 ℃ in 4 districts, 170 ℃ in 5 districts; 180 ℃ in 6 districts, 190 ℃ in 7 districts, 185 ℃ in 8 districts, 200 ℃ in 9 districts; Head temperature is set at 205 ℃, melt extrudes, and will extrude the product granulation and be placed in the injection moulding machine, obtains sample S4 through injection moulding.
Comparative Examples 1
This Comparative Examples is used for comparative illustration fire retardant material disclosed by the invention and preparation method thereof.
The preparation method of fire retardant material is identical with embodiment 7, and different is not add A3.
Prepare sample D1.
Comparative Examples 2
This Comparative Examples is used for comparative illustration fire retardant material disclosed by the invention and preparation method thereof.
The preparation method of fire retardant material is identical with embodiment 7, and different is, does not add A3, and the addition of white lake is 150 weight parts.
Prepare sample D2.
Performance test
Above fire retardant material sample S1-S4, D1, the D2 for preparing carried out following performance test:
1, combustionproperty
The combustionproperty that adopts the UL94 standard to test fire retardant material;
2, tensile strength
Adopt ASTM D638 method to measure the tensile strength of fire retardant material;
3, flexural strength and modulus in flexure
Adopt ASTM D790 method to measure the flexural strength and the modulus in flexure of fire retardant material;
4, elongation at break
The mensuration interior material of employing ASTM D638 method mensuration fire retardant material;
5, notched Izod impact strength
Adopt ASTM D256 method to measure the notched Izod impact strength of fire retardant material; Test result is seen table 1.
Table 1
| Sample | S1 | S2 | S3 | S4 | D1 | D2 |
| Combustionproperty | V-2 | V-1 | V-0 | V-0 | V-2 | V-2 |
| Whether burning drips | Not | Not | Not | Not | Be | Not |
| Tensile strength | 17.2 | 16.1 | 16.03 | 15.95 | 15.2 | 13.16 |
| Flexural strength | 24.23 | 24.13 | 24.19 | 23.83 | 24.58 | 23.98 |
| Modulus in flexure | 1367.2 | 1345.4 | 1239.41 | 1230 | 1424.3 | 1200.49 |
| Elongation at break | 19.8 | 20.5 | 19.2 | 18.6 | 15.2 | 12.93 |
| Notched Izod impact strength | 18.5 | 15.6 | 17.68 | 18.08 | 17.9 | 33.18 |
Can find out from the test result of table 1; Adopt organic complex disclosed by the invention and the acting in conjunction of oxyhydroxide fire retardant, can play the obvious synergistic effect, when guaranteeing flame retardant properties; Greatly reduce the addition of oxyhydroxide fire retardant, thereby guaranteed the mechanical property of fire retardant material.
The above is merely preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of within spirit of the present invention and principle, being done, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (16)
1. an organic complex has the structure shown in the formula 1,
Formula 1:
Wherein, R1 is selected from a kind of in two (the two amidine propane) dihydrochlorides of Diisopropyl azodicarboxylate, ABVN, azo, the azo two isopropylformic acid dimethoxy nitriles; R2 is selected from the alkyl or alkenyl that carbonatoms is 1-4, and R3 is selected from a kind of in alkyl that hydrogen, carbonatoms are 1-4, the thiazolinyl that carbonatoms is 1-4; M is the ion of complexing metal, and said complexing metal is selected from a kind of in IVB family or the VIIB family metal; N is selected from the integer of 1-100.
2. organic complex according to claim 1 is characterized in that, said R1 is a Diisopropyl azodicarboxylate; R2 is selected from the alkyl or alkenyl that carbonatoms is 2-3, and R3 is selected from hydrogen or carbonatoms is the alkyl of 2-3; M is selected from a kind of in mn ion, iron ion, cobalt ion, nickel ion, zine ion, the cupric ion; N is selected from the integer of 10-90.
3. the preparation method of organic complex as claimed in claim 1 comprises:
A, monomer, linking agent and initiator are mixed, and under heating condition, react; Wherein, Said monomer is N-(4-aminomethyl phenyl) acrylamide monomer and/or N-(p-hydroxy phenyl) acrylamide monomer; Said linking agent is selected from 4; 4 '-in the amino disulfoxide of two (acrylic amide) sulfobenzide, Trimethylsulfoxonium Iodide, DMSO 99.8MIN., 2-, tetramethylene sulfone one or more, said initiator is selected from one or more in Diisopropyl azodicarboxylate, ABVN, two (the two amidine propane) dihydrochlorides of azo, the azo two isopropylformic acid dimethoxy nitriles;
B, under heating condition, the salts solution of complexing metal is splashed in the above-mentioned product, and stirs, said complexing metal is selected from a kind of in IVB family or the VIIB family metal;
C, with the product of step b through filtering, washing, and filtering once more and get final product.
4. preparation method according to claim 3 is characterized in that, the temperature that heats among the step a is 40-80 ℃, and the reaction times is 5-40min; The temperature that heats among the step b is 40-80 ℃.
5. preparation method according to claim 3 is characterized in that, said monomer is N-(4-aminomethyl phenyl) acrylamide monomer, said linking agent is 4,4 '-two (acrylic amide) sulfobenzide, said initiator is 4,4 '-two (acrylic amide) sulfobenzide.
6. according to any described preparation method in the claim 3,4,5, it is characterized in that in step a, the mol ratio of said monomer and linking agent, initiator is 0.05-1: 0.01-1: 1.
7. according to any described preparation method in the claim 3,4,5, it is characterized in that the salt of said complexing metal is soluble sulphate, nitrate salt, muriate or acetate a kind of in manganese, iron, cobalt, nickel, zinc, the copper.
8. preparation method according to claim 7 is characterized in that, in step b, in the molar content of complexing metal, the salt of complexing metal and monomeric mol ratio are 0.01-1: 1.
9. according to any described preparation method in the claim 3,4,5,8, it is characterized in that; In the salts solution of said complexing metal, the concentration of the salt of complexing metal is 0.05-1mol/l.
10. fire retardant material; Comprise matrix resin, fire retardant and organic complex; Wherein, said matrix resin is a polyolefine, and said fire retardant is the oxyhydroxide fire retardant; Said organic complex is claim 1 or 2 described organic complexs, and perhaps said organic complex is the product that the described method of claim 3-9 prepares.
11. fire retardant material according to claim 10 is characterized in that, is benchmark with the content of said matrix resin, the content of said fire retardant is 5-60wt%, and the content of said organic complex is 2-25wt%.
12. according to claim 10 or 11 described fire retardant materials, it is characterized in that, also contain in oxidation inhibitor, compatilizer, the coupling agent one or more in the said fire retardant material; Content with said matrix resin is benchmark, and the content of said oxidation inhibitor is 0-1wt%, and the content of said compatilizer is 0-5wt%, and the content of said coupling agent is 0-5wt%, and the content of said oxidation inhibitor, compatilizer, coupling agent is not 0 simultaneously.
13. fire retardant material according to claim 12 is characterized in that, said matrix resin is a Vestolen PP 7052, and said oxyhydroxide fire retardant is selected white lake for use; Contain oxidation inhibitor, compatilizer and coupling agent in the said fire retardant material simultaneously; Content with said matrix resin is benchmark, and the content of said oxidation inhibitor is 0.1-0.5wt%, and the content of said compatilizer is 0.5-4wt%, and the content of said coupling agent is 0.5-4wt%.
14. the preparation method of fire retardant material as claimed in claim 10; Comprise: the raw mix that will contain said matrix resin, fire retardant and organic complex joins in the forcing machine; The control extruder temperature is 160-220 ℃, and head temperature is 200-220 ℃, and screw speed is 50-350rpm; Rate of feeding is that 10-50rpm extrudes, and obtains fire retardant material through granulation, injection moulding then.
15. preparation method according to claim 14 is characterized in that, join said raw mix in the forcing machine before, also comprise earlier said matrix resin, fire retardant and organic complex mixed 5-20min down at 40-120 ℃.
16. according to claim 14 or 15 described preparing methods, it is characterized in that, also contain in oxidation inhibitor, compatilizer, the coupling agent one or more in the said raw mix; Content with said matrix resin is benchmark, and the content of said oxidation inhibitor is 0-1wt%, and the content of said compatilizer is 0-5wt%, and the content of said coupling agent is 0-5wt%, and the content of said oxidation inhibitor, compatilizer, coupling agent is not 0 simultaneously.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102748428A CN102382253A (en) | 2010-08-31 | 2010-08-31 | Organic complex and preparation method thereof as well as flame-retarding material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102748428A CN102382253A (en) | 2010-08-31 | 2010-08-31 | Organic complex and preparation method thereof as well as flame-retarding material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102382253A true CN102382253A (en) | 2012-03-21 |
Family
ID=45822133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102748428A Pending CN102382253A (en) | 2010-08-31 | 2010-08-31 | Organic complex and preparation method thereof as well as flame-retarding material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102382253A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4939635A (en) * | 1972-08-23 | 1974-04-13 | ||
| JPS6411145A (en) * | 1987-07-03 | 1989-01-13 | Hitachi Cable | Flame-retardant electrically insulating composition |
| JPH04224836A (en) * | 1990-12-26 | 1992-08-14 | Nippon Soda Co Ltd | Flame retardant and flame-retarding resin composition |
| CN1757667A (en) * | 2005-11-08 | 2006-04-12 | 四川大学 | Halogen-free expansion type retardant polyethylene contg. organic metal complex |
| CN1865333A (en) * | 2006-06-26 | 2006-11-22 | 四川大学 | Halogen-free reaction extruded expansible flame-proof polythene comprising organic metal complex and its preparation method |
-
2010
- 2010-08-31 CN CN2010102748428A patent/CN102382253A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4939635A (en) * | 1972-08-23 | 1974-04-13 | ||
| JPS6411145A (en) * | 1987-07-03 | 1989-01-13 | Hitachi Cable | Flame-retardant electrically insulating composition |
| JPH04224836A (en) * | 1990-12-26 | 1992-08-14 | Nippon Soda Co Ltd | Flame retardant and flame-retarding resin composition |
| CN1757667A (en) * | 2005-11-08 | 2006-04-12 | 四川大学 | Halogen-free expansion type retardant polyethylene contg. organic metal complex |
| CN1865333A (en) * | 2006-06-26 | 2006-11-22 | 四川大学 | Halogen-free reaction extruded expansible flame-proof polythene comprising organic metal complex and its preparation method |
Non-Patent Citations (1)
| Title |
|---|
| A.B.SHEHATA*: "A new cobalt chelate as flame retardant for polypropylene filled with magnesium hydroxide", 《POLYMER DEGRADATION AND STABILITY》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101910299B (en) | Flameproof thermoplastic resin composition and method for preparing the same | |
| CN101353458B (en) | Halogen-free expansion type flame-retardant and preparation thereof | |
| EP0307802B1 (en) | Thermoplastic resin composition and method for preparing the same | |
| KR100191796B1 (en) | Method for preparing modified resins and their applications | |
| JP3721200B2 (en) | Thermoplastic resin composition | |
| JP3547910B2 (en) | Flame retardant polymer composition | |
| JP4784198B2 (en) | Thermosetting resin composition | |
| EP0459766B1 (en) | Modified polyolefincontaining thermoplastic resin composition | |
| JP2008501063A (en) | Phosphorus-containing compounds useful for the production of halogen-free refractory polymers | |
| CN103289290B (en) | A kind of phosphorus system synergistic flame-retardant ABS compound material and preparation method thereof | |
| CN103402914B (en) | The manufacture method of oxidation sheet graphite derivative, its resin composite materials and this resin composite materials | |
| JPWO2019093066A1 (en) | Flame Retardant Composition and Flame Retardant Thermoplastic Resin Composition Containing The Flame Retardant Composition | |
| WO2009082096A2 (en) | Flame-retardant polyester resin composition having excellent heat resistance | |
| JPH0211658A (en) | Thermoplastic molding material based on functional polyphenylene ether and polyamide | |
| US6231965B1 (en) | Polycarbonate/polyolefin resin composition, process for producing the same, and moldings | |
| CN102382253A (en) | Organic complex and preparation method thereof as well as flame-retarding material and preparation method thereof | |
| CN104072927A (en) | Special reinforced regenerated flame-retardant HIPS (high impact polystyrene) for home appliances and preparation technique thereof | |
| CN110305382A (en) | A kind of halogen-free flameproof automotive wire bundle cable feed composition | |
| JP3310088B2 (en) | Thermoplastic resin composition | |
| CN107698943A (en) | A kind of high-heat-resisting glass-fiber reinforced polyester composite material and preparation method thereof | |
| JP2002212564A (en) | Flame retardant, method for producing the same and flame-retardant resin composition containing the flame retardant | |
| EP0691374A1 (en) | Reinforced, flame-resistant thermoplastic composition | |
| US6120709A (en) | Electroconductive resin composition | |
| KR100443269B1 (en) | A polyolefin resin composition with improved flame retardancy | |
| JPH11302512A (en) | Flame-retardant resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120321 |