CN105419317A - Novel nylon 6-polybutylene terephthalate flame retardant alloy material and preparation method thereof - Google Patents
Novel nylon 6-polybutylene terephthalate flame retardant alloy material and preparation method thereof Download PDFInfo
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- CN105419317A CN105419317A CN201510995544.0A CN201510995544A CN105419317A CN 105419317 A CN105419317 A CN 105419317A CN 201510995544 A CN201510995544 A CN 201510995544A CN 105419317 A CN105419317 A CN 105419317A
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- kaolin
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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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- 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
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
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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
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
Belonging to the technical field of high polymer materials, the invention provides a novel nylon 6-polybutylene terephthalate flame retardant alloy material and a preparation method thereof. According to the invention, an appropriate formula process is adopted, and a unique compound flame retardant is employed for cooperation to prepare the environment-friendly high-performance flame retardant PA6-PBT alloy material, compared with general PBT/PA6 flame retardant materials, the alloy material has obvious advantages in the aspects of rigidity, toughness, heat resistance, flame resistance and dimensional stability, and is easy for molding processing. Also, the added modified kaolin is well compatible with all polymers, the alloy material can stably pass the UL94-V0 flame retardant grade, can stably pass 850DEG C glowing filaments without fire breakout, also can satisfy a lot of occasions with high flame retardant level and performance requirements, and is widely applicable to capacitor shells, load break switches, motor shells, terminal boards, coil skeletons, plugs and circuit connectors, telephone distribution boxes and other low voltage electrical apparatuses.
Description
Technical field
The invention belongs to technical field of polymer materials, particularly relate to a kind of Modification of kaolin nylon 6-polybutylene terephthalate alloy material and preparation method thereof.
Background technology
Nylon 6 (having another name called polyamide 6, PA6) is a kind of engineering plastics, has excellent mechanical property and electrical property, also has the advantages such as wear-resisting, oil resistant, self-lubricating, corrosion-resistant and good processing characteristics.But the water-absorbent of PA6 is large, low temperature and dry state poor impact toughness, poor dimensional stability, makes its range of application be subject to certain restrictions.
Polybutylene terephthalate (PBT) is the thermoplastic polyester that 20 century 70s grow up, there is excellent machinery, electric, high temperature resistant, moisture-proof, resistance to chemical attack, electrical insulation capability be good, good elasticity, crystallization velocity fast, good fluidity and be easy to the features such as forming process, and can good mechanical property be kept in wide temperature range.Due to the performance of PBT product uniqueness, PBT engineering plastics and various alloy are widely used in electric, automobile, machinery, instrument, light textile and the every field such as civilian, are a kind of indispensable type materials.Along with the progress of science and technology and the development of industry, higher requirement be it is also proposed to the application of material, require higher intensity, higher precision, flame retardant properties, environmental protection, low cost etc.And PBT exists the shortcomings such as large, the easy warpage of molding shrinkage, notch shock sensitivity, this has just driven the development of modified PBT material and PBT alloy.
Modified nylon-6 material can be widely used in the industry such as power tool and electric connector; Modified PBT is also widely used in electronics, automobile and household electrical appliance.Advantage in conjunction with PA6 and PBT prepares blend, makes up respective defect, thus obtains the alloy material of high comprehensive performance, can be used for high performance engineering plastics.
Often use glass fiber reinforcement in PBT/PA6 alloy in current research, cause flame retardant properties to be deteriorated although enhance mechanical property, need large fire retardant addition just can reach corresponding flame retardant effect, thus cause the over-all properties of alloy material poor.
For this reason, the present invention prepares the novel PBT/PA fire retardant alloy material with low warpage excellent combination property by modified kaolin and compound flame retardant technology.
Summary of the invention
The invention provides a kind of Modification of kaolin nylon 6-polybutylene terephthalate alloy material and preparation method thereof.
The present invention is achieved by the following technical programs.
A kind of Modification of kaolin nylon provided by the invention 6-polybutylene terephthalate alloy material is made up of the component of following weight part: the polybutylene terephthalate (PBT) of 10 ~ 60 parts, the modification of nylon 6 (PA6) of 90 ~ 40 parts, the compatilizer of 0.5 ~ 2 part, the tensio-active agent of 1 part ~ 5 parts, the compound flame retardant of 10 ~ 25 parts, the modified kaolin of 5 ~ 15 parts, the antioxidant of 0.5 ~ 0.8 part.
Further, described compatilizer is the one in epoxy resin CYD-011, epoxy resin E-54.
Further, described tensio-active agent is the one in stearyl dimethyl benzyl ammonium chloride (tensio-active agent 1827), dodecyl benzyl dimethyl ammonium chloride (tensio-active agent 1227), sodium lauryl sulphate (SDS) or cetyl trimethylammonium bromide (CTAB).
Further, the method for modifying of described modified kaolin is: kaolin is first through urea intercalation, and sulfuric acid is peeled off, then through silane resin acceptor kh-550 and surfactant-modified, obtained after ultrasonic agitation.
1) first kaolin and a certain amount of urea soln are mixed with a certain proportion of suspension, constant temperature is kept when then rising to 35 DEG C ~ 100 DEG C, electric mixer stirs, reaction 5 ~ 72h, then rinse the urea of remained on surface with a large amount of dehydrated alcohol, after decompress filter, the kaolin/urea complex of filtration is dried under 40 ~ 70 DEG C of conditions, pulverize, obtain intercalation kaolin soil;
2) get intercalation kaolin soil appropriate, add the aqueous solution that a certain amount of PH is 1-6, use ultrasonic wave to carry out supersound process after mixing immediately, the temperature for the treatment of processes is 50-80 DEG C, and the time length is 5-30min; Then washes of absolute alcohol is used 2 ~ 3 times, dry at 60 DEG C, pulverize, obtain peeling off kaolin;
3) stripping kaolin, distilled water are mixed with suspension according to mass ratio 1:2, add tensio-active agent, then be put in heat collecting type constant-temperature heating magnetic stirring apparatus, constant temperature is kept when temperature rises to 50-90 DEG C, dropwise add silane coupling agent (KH550) and the dehydrated alcohol solution that dilute of 1:3 react 2h under constant temperature by volume again, it is native that in whole solution, silane coupling agent (KH550) is the last suction filtration of kaolinic 2%-5%, drying, grinding obtain the intercalation kaolin of surface modification.
Aforesaid method carries out modification to kaolin, makes the sheet interlayer spacing of modified kaolin be more than 1nm, and intercalation rate is more than 80%, activation index more than 80%, can be compatible well with polymkeric substance; Adopt nontoxic intercalator urea simultaneously, peel off kaolin and adopt ultrasonic acid hydrolyzation, fast effectively.
Further, described compound flame redundant forms by the raw material of following weight part is composite: the ammonium polyphosphate (APP) of 20 ~ 75 parts, the tetramethylolmethane (PER) of 5 ~ 25 parts, the compound melamine cyanurate (MC-602) of 30 ~ 80 parts.Adopt ammonium polyphosphate (APP): fire retardant that/tetramethylolmethane (PER)/compound melamine cyanurate (MC-602) forms use nitrogen phosphorus synergy to PBT, PA extremely alloy there is environmental protection low stain, improve flame retarding efficiency and fire retardant addition simultaneously.
Further, described antioxidant is the one in antioxidant 1098, antioxidant 1010, and antioxidant improves the antioxidant property of matrix material.
Present invention also offers the preparation method of a kind of kaolin reinforced nylon 6-polybutylene terephthalate alloy material, comprise the following steps:
1) raw material drying pre-treatment, by more than the 12h under 80 ~ 100 DEG C of environment of polybutylene terephthalate (PBT) and modification of nylon 6 (PA6); By compatilizer, compound flame retardant, modified kaolin, antioxidant dry more than 12h at 50 ~ 75 DEG C of temperature;
2) above-mentioned dried feed joined in high-speed mixer by proportioning and fully mix, stirring at normal temperature 3 ~ 5min, enters Banbury mixer after mixing, banburying 5 ~ 10min, and rotating speed is 50 ~ 70r/min;
3) put into the mould of standard, with vulcanizing press preheating 3 ~ 10min at 200 ~ 240 DEG C, keep at least 3min be forced into 5 ~ 6MPa after sample melts gradually after, exhausted air, two to three times repeatedly; At least 3min is kept, finally naturally cooling under room temperature on cooling plate after continuing to be forced into 10MPa.
Beneficial effect of the present invention is: the present invention adopts suitable Recipe, and be equipped with unique compound flame retardant, prepare the high-performance refractory PA6-PBT alloy material of environmental protection flame retardant, this alloy material is compared to the fire-retardant enhancing alloy of PBT/PA6, in rigidity, toughness, resistance toheat, flame retardant resistance and dimensional stability, there is outstanding advantage, and be easy to forming process; Add modified kaolin simultaneously, can be compatible well with each polymkeric substance, the flame retardant rating by UL94 mono-V0 that alloy energy is stable, what energy was stable can not be on fire by 850 DEG C of glowing filaments, many fire-retardant ranks and the higher occasion of performance requriements can be met, be widely used in capacitor case, load break switch, motor case, terminal strip, coil rack, plug and electric cupler, in the low-voltage apparatuses such as phone distributor box.
Embodiment
Further describe technical scheme of the present invention below, but described in claimed scope is not limited to.
Embodiment one
A kind of kaolin reinforced nylon 6-polybutylene terephthalate alloy material provided by the invention and preparation method thereof, specific as follows:
1, raw material prepares:
Polybutylene terephthalate (PBT);
Modification of nylon 6 (PA6);
Compatilizer: the one of epoxy resin CYD-011, epoxy resin E-54, the present embodiment selects epoxy resin CYD-011;
The compound melamine cyanurate (MC-602) of the ammonium polyphosphate (APP) of compound flame retardant: 20kg, the tetramethylolmethane (PER) of 5kg and 30kg is composite to be formed;
Antioxidant: the one in antioxidant 1098 (N, N'-pair-(3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine), antioxidant 1010, the present embodiment selects antioxidant 1098;
Modified kaolin, its method of modifying is:
1) first kaolin and 18mol/L urea soln are mixed with the suspension of mass ratio 1:10, then be put in water-bath, constant temperature is kept when temperature rises to 65 DEG C, electric mixer stirs, and reaction 72h, then rinses the urea of remained on surface with a large amount of dehydrated alcohol, after decompress filter, kaolin/the urea complex of filtration is dried under 60 DEG C of conditions, pulverizes, obtain intercalation kaolin soil;
2) get intercalation kaolin soil appropriate, add 100ml, in 1mol/L sulphuric acid soln, use ultrasonic wave to carry out supersound process after mixing immediately, the temperature for the treatment of processes is 50-80 DEG C, and the time length is 5-30min; Then washes of absolute alcohol is used 2 ~ 3 times, dry at 60 DEG C, pulverize, obtain peeling off kaolin;
3) stripping kaolin, distilled water are mixed with suspension according to mass ratio 1:2, then add the cetyl trimethylammonium bromide (CTAB) that quality is kaolin 3% is put in heat collecting type constant-temperature heating magnetic stirring apparatus, constant temperature is kept when temperature rises to 50-90 DEG C, dropwise add silane coupling agent (KH550) and the dehydrated alcohol solution that dilute of 1:3 react 2h under constant temperature by volume again, it is native that in whole solution, silane coupling agent (KH550) is the last suction filtration of kaolinic 2%-5%, drying, grinding obtain the intercalation kaolin of surface modification.
2, raw material weighing
Take: 10kg polybutylene terephthalate (PBT), 60kg modification of nylon 6 (PA6), 0.5kg compatilizer, 10kg compound flame retardant, 5kg modified kaolin, 0.5kg antioxidant.
3, preparation method
1) raw material drying pre-treatment, by more than the 12h under 80 ~ 100 DEG C of environment of polybutylene terephthalate (PBT) and modification of nylon 6 (PA6); By compatilizer, compound flame retardant, modified kaolin, antioxidant dry more than 12h at 50 ~ 75 DEG C of temperature;
2) above-mentioned dried feed joined in high-speed mixer by proportioning and fully mix, stirring at normal temperature 3 ~ 5min, enters Banbury mixer after mixing, banburying 5 ~ 10min, and rotating speed is 50 ~ 70r/min;
3) put into the mould of standard, with vulcanizing press preheating 3 ~ 10min at 200 ~ 240 DEG C, keep at least 3min be forced into 5 ~ 6MPa after sample melts gradually after, exhausted air, two to three times repeatedly; At least 3min is kept, finally naturally cooling under room temperature on cooling plate after continuing to be forced into 10MPa.
Embodiment two ~ embodiment eight
Raw material and the consumption of the use of embodiment two ~ embodiment eight are different from embodiment, and the preparation method of the method for modifying of modified kaolin and kaolin reinforced nylon 6-polybutylene terephthalate alloy material is with embodiment one.The raw material of the use of embodiment two ~ embodiment eight and consumption are as following table 1:
Table 1
Wherein the formula of compound flame retardant is as follows:
Table 2
Claims (9)
1. Modification of kaolin nylon 6-polybutylene terephthalate alloy composite materials, is characterized in that: be made up of the component of following weight part: the polybutylene terephthalate (PBT) of 10 ~ 20 parts, the modification of nylon 6 (PA6) of 60 ~ 80 parts, 0.5 ~ 2 part of ground compatilizer, the tensio-active agent of 1 part ~ 5 parts, the compound flame retardant of 10 ~ 25 parts, the modified kaolin of 5 ~ 15 parts, antioxidant of 0.5 ~ 0.8 part.
2. Modification of kaolin nylon 6-polybutylene terephthalate alloy material as claimed in claim 1, is characterized in that: described ground compatilizer is the one in epoxy resin CYD-011, epoxy resin E-40.
3. Modification of kaolin nylon 6-polybutylene terephthalate alloy material as claimed in claim 1, is characterized in that: described tensio-active agent is the one in stearyl dimethyl benzyl ammonium chloride (tensio-active agent 1827), dodecyl benzyl dimethyl ammonium chloride (tensio-active agent 1227), sodium lauryl sulphate (SDS) or cetyl trimethylammonium bromide (CTAB).
4. kaolin reinforced nylon 6-polybutylene terephthalate alloy material as claimed in claim 1, it is characterized in that: the method for modifying of described modified kaolin is: kaolin is first through urea intercalation, sulfuric acid is peeled off, then through silane resin acceptor kh-550 and surfactivity cetyl trimethylammonium bromide (CTAB) surface modification gained.
5. kaolin reinforced nylon 6-polybutylene terephthalate alloy material as claimed in claim 1, is characterized in that: the acidity of solution required in the modification of described modified kaolin is PH1-6.
6. kaolin reinforced nylon 6-polybutylene terephthalate alloy material as claimed in claim 1, is characterized in that: technique required in the modification of described modified kaolin is acid system and certain ultrasonic velocity and time.
7. kaolin reinforced nylon 6-polybutylene terephthalate alloy material as claimed in claim 1, is characterized in that: described compound flame redundant forms by the raw material of following weight part is composite: the ammonium polyphosphate (APP) of 10 ~ 75 parts, the tetramethylolmethane (PER) of 5 ~ 25 parts, the compound melamine cyanurate (MC-602) of 5 ~ 80 parts.
8. kaolin reinforced nylon 6-polybutylene terephthalate alloy material as claimed in claim 1, is characterized in that: described antioxidant is the one in antioxidant 1098, antioxidant 1068 or antioxidant 1010.
9. a preparation method for the kaolin reinforced nylon 6-polybutylene terephthalate alloy material as described in claim 1 ~ 6 any one, is characterized in that: comprise the following steps:
1) raw material drying pre-treatment, by more than the 12h under 80 ~ 100 DEG C of environment of polybutylene terephthalate (PBT) and modification of nylon 6 (PA6); By compatilizer, compound flame retardant, modified kaolin, antioxidant dry more than 12h at 50 ~ 75 DEG C of temperature;
2) above-mentioned dried feed joined in high-speed mixer by proportioning and fully mix, stirring at normal temperature 1 ~ 10min, enters Banbury mixer after mixing, banburying 5 ~ 10min, and rotating speed is 50 ~ 70r/min;
3) put into the mould of standard, with vulcanizing press preheating 3 ~ 10min at 200 ~ 240 DEG C, keep at least 3min be forced into 5 ~ 6MPa after sample melts gradually after, exhausted air, two to three times repeatedly; At least 3min is kept, finally naturally cooling under room temperature on cooling plate after continuing to be forced into 10MPa.
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Cited By (4)
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| CN106497031A (en) * | 2016-10-09 | 2017-03-15 | 武汉理工大学 | A kind of flame-proof PA 6/PBT composite and preparation method thereof |
| CN108098092A (en) * | 2017-12-21 | 2018-06-01 | 成都川美新技术股份有限公司 | A kind of method being sintered using solder(ing) paste to radio frequency substrate and housing |
| CN109439608A (en) * | 2018-11-16 | 2019-03-08 | 安徽骏旌环保科技有限公司 | A kind of duck class excrement decomposition culture medium |
| CN109575552A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | Functional flame-retardant high-molecular composition and its preparation method and application |
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| CN106497031A (en) * | 2016-10-09 | 2017-03-15 | 武汉理工大学 | A kind of flame-proof PA 6/PBT composite and preparation method thereof |
| CN109575552A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | Functional flame-retardant high-molecular composition and its preparation method and application |
| CN108098092A (en) * | 2017-12-21 | 2018-06-01 | 成都川美新技术股份有限公司 | A kind of method being sintered using solder(ing) paste to radio frequency substrate and housing |
| CN109439608A (en) * | 2018-11-16 | 2019-03-08 | 安徽骏旌环保科技有限公司 | A kind of duck class excrement decomposition culture medium |
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Application publication date: 20160323 |