CN105936712A - Hard flame-retardant optical cable material and preparation method thereof - Google Patents
Hard flame-retardant optical cable material and preparation method thereof Download PDFInfo
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- CN105936712A CN105936712A CN201610457183.9A CN201610457183A CN105936712A CN 105936712 A CN105936712 A CN 105936712A CN 201610457183 A CN201610457183 A CN 201610457183A CN 105936712 A CN105936712 A CN 105936712A
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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
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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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
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- C08K2201/011—Nanostructured additives
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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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
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- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The invention discloses a hard flame-retardant optical cable material, which is composed of the following raw materials in parts by weight: 6 to 7 parts of amino guanidine sulfonate, 20 to 23 parts of carbon nanotubes, 0.3 to 0.4 part of N,N'-dicyclohexylcarbodiimide, 4 to 5 parts of phosphonitrilic chloride trimer, 0.2 to 0.4 part of sodium hydroxide, 1 to 2 parts of thiourea, 17 to 20 parts of nylon, 120 to 130 parts of polyvinyl chloride, and 5 to 7 parts of epoxy soybean oil. The provided optical cable material has the advantages of high surface strength and hardness, and strong impact resistant performance.
Description
Technical field
The present invention relates to mass technical field, particularly relate to a kind of hard fire-retardant cable material and preparation method thereof.
Background technology
Nanotechnology is in the eighties rise in last century, and is widely used in multiple fields.Research finds, adds after nanoparticle in the polymer, can the performance of significantly lift-off material.Such as when adding the nanoparticles such as a small amount of graphite skilful, CNT, molybdenum bisuphide in polymer, the mechanical strength of material will be obviously improved IWI.Research finds, only adds minimal amount of nano material and the HRR of material combustion just can be greatly reduced, the most also can the mechanical strength of lift-off composite.The nano flame retardant system that research is relatively more at present mainly has several: (1) inorganic nano-particle, such as nanometer ammoxidation town, nanometer ammoxidation lead and nano silicon etc..This based flame retardant is relatively low due to himself flame retarding efficiency, and fire retardant mechanism also with other nanoparticle difference, needs bigger addition, therefore can not be classified as flame retardant nano-materials completely when reality is applied.And the filling of filler also can produce impact to the mechanical property of material self.(2) laminated inorganic matter, such as nanoclay, brucite, expansible graphite etc..(3) pipe carbon and acicular nanoparticles, such as CNT, halloysite nanotubes and meerschaum etc..The tenth day of lunar month year in 21 century, the focus nano flame retardant technology having a large amount of report galapectite in recent years about polymer/carbon nano-tube flame-retardant system and meerschaum to be increasingly becoming research occurs two during the last ten years, although gradually growing up and achieve a series of achievement in research, but the polymeric material of nanorize combustion to extensively application, still has very long road to walk from research；
About the application in the polymer of nano flame retardant technology, some problem following is currently mainly had to need to solve: 1. nano fire-retarding additive significant advantage is that in trying for taper calorimetric, HRR reduces for a lot of nanoparticles, it is only necessary to add few amount and just the HRR of material combustion can be greatly reduced by W.But effect is tested significantly for traditional fire-retardant trial work section, such as oxygen index (OI) and vertical combustion, the most also can play negative effect.Therefore, need to consider nanoparticle to be modified or reaches the effect of cooperative flame retardant by compounding use with conventional flame retardant.The most in recent years, nanometer particle-modified research is got more and more, the particularly intercalation modifying to nanoclay.But the intercalation modifying agent of existing frequently-used nanoclay is the burning base amine salt of long-chain mostly, lacks and be specifically designed to flame-retardant modified intercalator or surface modifier.And most modifying agent itself does not have anti-flammability, some self the most flammable；Heat stability is the most poor, and initial decomposition degree is low, and difficulty is applicable to engineering plastics etc. and irons and melt the polymer that temperature is higher.Therefore, it is a direction of future studies for having nanometer particle-modified dose of anti-flammability and heat stability concurrently.3. having clear and definite fire retardant mechanism from the fire retardant such as halogen flame, phosphor nitrogen combustion inhibitor different, present stage lacks the explanation of system to the mechanism of nano flame retardant.Current approved mechanism mainly has the obstruct mechanism of the radical-scavenging mechanism of nanoclay, solid phase；Synergistic catalytic mechanism with expanding fire retardant；The network structure of CNT intercepts the impact etc. in mechanism and combustion process on system rheological characteristic.Therefore, the elaboration for nanoparticle fire retardant mechanism during polymer combustion will be the direction of future studies, and CNT lacks polar functional group due to surface simultaneously, and the compatibility with polymeric matrix is poor；The structure of high length-diameter ratio can cause the winding in the course of processing, gathering, thus is difficult to well disperse.Additionally, CNT only has obvious effect to reduction HRR, but can not effectively put forward oxygen index (OI) and the vertical combustion grade of material.In order to improve the CNT compatibility in the polymer and dispersibility, can use coupling agent, surfactant or polymer etc. that CNT is carried out surface to change, but class method of modifying often difficulty puies forward its fire resistance, some even can destroy original anti-flammability；.
Summary of the invention
The object of the invention is contemplated to make up the defect of prior art, it is provided that a kind of hard fire-retardant cable material and preparation method thereof.
The present invention is achieved by the following technical solutions:
A kind of hard fire-retardant cable material, it is made up of the raw material of following weight parts:
Guanidine Sulfamate 99 6-7, CNT 20-23, N, N'-Dicyclohexylcarbodiimide 0.3-0.4, hexachlorocyclotriph,sphazene 4-5, sodium hydroxide 0.2-0.4, thiourea 1-2, nylon 17-20, polrvinyl chloride 120-130, epoxy soybean oil 5-7.
A kind of preparation method of described hard fire-retardant cable material, it is made up of the raw material of following weight parts:
(1) above-mentioned CNT is joined in the mixed acid solution of its weight 80-100 times, described nitration mixture is made up of the sulphuric acid of the 96-98% that mass ratio is 3-4:1 and the hydrochloric acid solution of 87-90%, at 50-60 DEG C ultrasonic 17-20 minute, filter, precipitation is washed 2-3 time, it is vacuum dried 30-40 minute at 70-76 DEG C, obtains acidifying CNT；
(2) taking the 47-50% of above-mentioned acidifying carbon nanotubes, with Guanidine Sulfamate 99, N, N'-Dicyclohexylcarbodiimide mixes, join in the DMF of compound weight 70-80 times, ultrasonic 100-120 minute, send in reactor, be passed through nitrogen, rise high-temperature and be 120-127 DEG C, insulation reaction 35-40 hour, discharging, by product sucking filtration, with washing with acetone 3-4 time, it is placed in the baking oven of 70-80 DEG C and is dried to constant weight, obtain sulfonic acid guanidine grafting carbon nanotube；
(2) by remaining acidifying CNT, hexachlorocyclotriph,sphazene, sodium hydroxide mixing, join in the oxolane of compound weight 60-70 times, ultrasonic 100-110 minute, send in reactor, it is passed through nitrogen, rise high-temperature and be 68-70 DEG C, insulation reaction 35-40 hour, discharging, by product sucking filtration, with washing with acetone 3-4 time, it is placed in the baking oven of 70-80 DEG C and is dried to constant weight, obtain ring three phosphonitrile grafting carbon nanotube；
(3) 10-16% of above-mentioned nylon weight is taken, add in its weight 20-27 times, 17-20% formalin, stirring mixing 20-30 minute, dropping concentration is the hydrochloric acid of 3-6mol/l, and regulation pH is 2-3, it is passed through nitrogen, it is heated to boiling, keeps boiling 57-60 minute, discharging, it is cooled to room temperature, obtains hydroxylating nylon liquid；
(4) by above-mentioned sulfonic acid guanidine grafting carbon nanotube, ring three phosphonitrile grafting carbon nanotube, the mixing of hydroxylating nylon liquid, preheat 4-6 minute at 87-90 DEG C, rise high-temperature and be 155-160 DEG C, insulated and stirred 3-4 minute, filter, precipitation oxolane is washed 2-3 time, is vacuum dried 30-40 minute at being placed in 70-80 DEG C, obtains modified nylon CNT；
(5) above-mentioned modified nylon CNT is mixed with remaining each raw material, stir, dry, put into screw extruder and melt extrude, cool down, sieve, obtain described mass.
nullThe invention have the advantage that the mass of the present invention has good fire-retardant fireproof performance，The present invention first uses Guanidine Sulfamate 99、The pre-nylon blending of CNT that chlorine ring three phosphonitrile is grafted respectively，Nylon after hydroxylating discharging can have the good compatibility with the CNT after grafting，Improve this composite dispersibility in finished cable material the most further，The fire retardant mechanism of this composite is: when nylon in combustion，CNT is at polymer melt surface aggregation，And form cancellated layer of charcoal，These netted carbon-coatings are fine and close and almost without hole，It is effectively prevented outside heat and the entrance of oxygen when burning，Such that it is able to effectively reduce HRR and mass loss rate，And the Guanidine Sulfamate 99 being grafted can be coated on carbon nano tube surface，Its catabolite contributes to CNT and forms the finest and close network structure layer of charcoal，Guanidine Sulfamate 99 self decomposes can produce ammonia，Ammonia can react again the degraded promoting nylon with nylon，Both are common produces substantial amounts of ammonia、The non-flammable compressive gas such as steam and carbon dioxide，Oxygen in dilute combustion district and fuel gas，Play the effect that gas phase is fire-retardant；Chlorine ring three phosphonitrile of grafting plays the effect of similar patch, the mesh of the netted layer of charcoal that filling carbon nano-pipe is formed, can form Cl-, and catch the free radical that burning produces in chlorine atom combustion process the most therein, thus terminate the chain reaction of combustion process, improve the fire resistance of finished-product material.The mass surface strength of the present invention is high, hardness is good, excellent in cushion effect.
Detailed description of the invention
A kind of hard fire-retardant cable material, it is made up of the raw material of following weight parts:
Guanidine Sulfamate 99 6, CNT 20, N, N' Dicyclohexylcarbodiimide 0.3, hexachlorocyclotriph,sphazene 4, sodium hydroxide 0.2, thiourea 1, nylon 17, polrvinyl chloride 120, epoxy soybean oil 5.
A kind of preparation method of described hard fire-retardant cable material, it is made up of the raw material of following weight parts:
(1) being joined by above-mentioned CNT in the mixed acid solution of its weight 80 times, described nitration mixture is made up of the sulphuric acid of 96% that mass ratio is 3:1 and the hydrochloric acid solution of 87%, at 50 DEG C ultrasonic 17 minutes, filter, precipitation is washed 2 times, is vacuum dried 30 minutes at 70 DEG C, obtains acidifying CNT；
(2) taking the 47% of above-mentioned acidifying carbon nanotubes, with Guanidine Sulfamate 99, N, N' Dicyclohexylcarbodiimide mixes, join in the DMF of compound weight 70 times, ultrasonic 100 minutes, sending in reactor, be passed through nitrogen, rising high-temperature is 120 DEG C, insulation reaction 35 hours, discharging, by product sucking filtration, with washing with acetone 3 times, it is placed in the baking oven of 70 DEG C and is dried to constant weight, obtain sulfonic acid guanidine grafting carbon nanotube；
(2) by remaining acidifying CNT, hexachlorocyclotriph,sphazene, sodium hydroxide mixing, join in the oxolane of compound weight 60 times, ultrasonic 100 minutes, send in reactor, it is passed through nitrogen, rising high-temperature is 68 DEG C, insulation reaction 35 hours, discharging, by product sucking filtration, with washing with acetone 3 times, it is placed in the baking oven of 70 DEG C and is dried to constant weight, obtain ring three phosphonitrile grafting carbon nanotube；
(3) take the 10% of above-mentioned nylon weight, add in its weight 20 times, the formalin of 17%, stirring mixing 20 minutes, dropping concentration is the hydrochloric acid of 3mol/l, regulation pH is 2, is passed through nitrogen, is heated to boiling, keeps boiling 57 minutes, discharging, is cooled to room temperature, obtains hydroxylating nylon liquid；
(4) by above-mentioned sulfonic acid guanidine grafting carbon nanotube, ring three phosphonitrile grafting carbon nanotube, the mixing of hydroxylating nylon liquid, preheat 4 minutes at 87 DEG C, rising high-temperature is 155 DEG C, insulated and stirred 3 minutes, filter, precipitation oxolane is washed 2 times, is placed at 70 DEG C vacuum drying 30 minutes, obtains modified nylon CNT；
(5) above-mentioned modified nylon CNT is mixed with remaining each raw material, stir, dry, put into screw extruder and melt extrude, cool down, sieve, obtain described mass.
Performance test:
Hot strength: 19.4 MPa；
Low temperature brittleness impact temperature (DEG C) :-30 DEG C are passed through；
Fire-retardant rank: V-0；
After 100 DEG C × 240h hot air aging: hot strength rate of change (%)-7.3；
Extension at break rate of change (%)-8.1.
Claims (2)
1. a hard fire-retardant cable material, it is characterised in that it is made up of the raw material of following weight parts:
Guanidine Sulfamate 99 6-7, CNT 20-23, N, N'-Dicyclohexylcarbodiimide 0.3-0.4, hexachlorocyclotriph,sphazene 4-5, sodium hydroxide 0.2-0.4, thiourea 1-2, nylon 17-20, polrvinyl chloride 120-130, epoxy soybean oil 5-7.
2. the preparation method of a hard fire-retardant cable material as claimed in claim 1, it is characterised in that it is made up of the raw material of following weight parts:
(1) above-mentioned CNT is joined in the mixed acid solution of its weight 80-100 times, described nitration mixture is made up of the sulphuric acid of the 96-98% that mass ratio is 3-4:1 and the hydrochloric acid solution of 87-90%, at 50-60 DEG C ultrasonic 17-20 minute, filter, precipitation is washed 2-3 time, it is vacuum dried 30-40 minute at 70-76 DEG C, obtains acidifying CNT；
(2) taking the 47-50% of above-mentioned acidifying carbon nanotubes, with Guanidine Sulfamate 99, N, N'-Dicyclohexylcarbodiimide mixes, join in the DMF of compound weight 70-80 times, ultrasonic 100-120 minute, send in reactor, be passed through nitrogen, rise high-temperature and be 120-127 DEG C, insulation reaction 35-40 hour, discharging, by product sucking filtration, with washing with acetone 3-4 time, it is placed in the baking oven of 70-80 DEG C and is dried to constant weight, obtain sulfonic acid guanidine grafting carbon nanotube；
(2) by remaining acidifying CNT, hexachlorocyclotriph,sphazene, sodium hydroxide mixing, join in the oxolane of compound weight 60-70 times, ultrasonic 100-110 minute, send in reactor, it is passed through nitrogen, rise high-temperature and be 68-70 DEG C, insulation reaction 35-40 hour, discharging, by product sucking filtration, with washing with acetone 3-4 time, it is placed in the baking oven of 70-80 DEG C and is dried to constant weight, obtain ring three phosphonitrile grafting carbon nanotube；
(3) 10-16% of above-mentioned nylon weight is taken, add in its weight 20-27 times, 17-20% formalin, stirring mixing 20-30 minute, dropping concentration is the hydrochloric acid of 3-6mol/l, and regulation pH is 2-3, it is passed through nitrogen, it is heated to boiling, keeps boiling 57-60 minute, discharging, it is cooled to room temperature, obtains hydroxylating nylon liquid；
(4) by above-mentioned sulfonic acid guanidine grafting carbon nanotube, ring three phosphonitrile grafting carbon nanotube, the mixing of hydroxylating nylon liquid, preheat 4-6 minute at 87-90 DEG C, rise high-temperature and be 155-160 DEG C, insulated and stirred 3-4 minute, filter, precipitation oxolane is washed 2-3 time, is vacuum dried 30-40 minute at being placed in 70-80 DEG C, obtains modified nylon CNT；
(5) above-mentioned modified nylon CNT is mixed with remaining each raw material, stir, dry, put into screw extruder and melt extrude, cool down, sieve, obtain described mass.
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| CN201610457183.9A CN105936712A (en) | 2016-06-22 | 2016-06-22 | Hard flame-retardant optical cable material and preparation method thereof |
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| CN201610457183.9A CN105936712A (en) | 2016-06-22 | 2016-06-22 | Hard flame-retardant optical cable material and preparation method thereof |
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Application publication date: 20160914 |