CN103834163B - Foamed polyurethane modified MC nylon matrix material and preparation method thereof - Google Patents
Foamed polyurethane modified MC nylon matrix material and preparation method thereof Download PDFInfo
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- CN103834163B CN103834163B CN201310642699.7A CN201310642699A CN103834163B CN 103834163 B CN103834163 B CN 103834163B CN 201310642699 A CN201310642699 A CN 201310642699A CN 103834163 B CN103834163 B CN 103834163B
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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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- 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
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
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- 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
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
Abstract
The present invention relates to foamed polyurethane modified MC nylon matrix material and preparation method thereof.The foamed polyurethane powder of the caprolactam monomer of 100 weight parts and 0.5 ~ 20 weight part is joined in container, dewater under vacuum conditions, as pressure <500Pa, add the basic catalyst of 0.005 ~ 0.5 weight part, continue to vacuumize, when system viscosity increases to the casting limit, remove vacuum, add the activator of 0.01 ~ 1 weight part, be then cast to rapidly in the mould of preheating, the demoulding, namely obtains the MC nylon composite materials of foamed polyurethane modification.In the present invention, due to the generation of PU and nylon 6 multipolymer, effectively improve the interface cohesion effect of two-phase, a small amount of PU just obviously can increase the resistance to impact shock of matrix material, toughness significantly improves, the requirements at the higher level of some industrial circle to material can be met, can better realize moulding Dai Gang, economizing on resources and reduce costs.
Description
Technical field
The invention belongs to engineering plastics field, particularly foamed polyurethane modified MC nylon matrix material and preparation method thereof.
Background technology
MC nylon is in the basic conditions, is formed through anionic ring-opening polymerization by caprolactam monomer, also known as monomer moulding casting nylon (Monomer casting nylon), is the one of engineering plastics.MC nylon products have lightweight, intensity is high, self-lubricating, wear-resisting, anticorrosion, the multiple special performances such as insulation, are almost applied to all industrial circles.It can the metal products prepared with materials such as copper, stainless steel, aluminium alloys of directly replacement part, " to mould Dai Gang, performance is remarkable ".But MC nylon also exists some shortcomings, as under dry state and low temperature, resistance to impact shock is low, product size poor stability, strength and stiffness and metallographic phase ratio, apart from comparatively large, present larger fragility, especially under cryogenic easier embrittlement.In order to address this problem, the method for physics or chemistry is normally adopted to carry out modification.Patent CN102146160A discloses the introducing by laurolactam monomer, makes the chemical structure of monomer moulding casting nylon and polymeric species change, to reach the object of toughening modifying.But when modified monomer moulding casting nylon is 2 ~ 3 times of conventional MC nylon in toughness, the used in amounts of laurolactam monomer will reach about 40% of caprolactam monomer mass parts.Patent CN102796256A discloses and adopts crosslinked polypropylene to carry out blending and modifying monomer moulding casting nylon, but the consumption of crosslinked polypropylene is when reaching 5 ~ 20% of caprolactam monomer mass parts, this method makes the resistance to impact shock of obtained modified monomer nylon monomer-cast nylon improve more than 70%.
Foamed polyurethane has lightweight, rebound resilience and excellent durability, density and hardness is adjustable, the characteristics such as shock-resistant, heat-proof quality is good, there is performance (reference " study and practice of urethane " such as easily carrying out cutting, perforation, bonding processing simultaneously, Chen Xuan, " chemical engineering abstracts " 2007,1).The waste hard foam plastics produced in industrial production, the general method of burning that adopts processes, and both wastes material, and causes environmental pollution again.Patent CN101096426A discloses and foams after mixing with polyether glycol, isocyanic ester after waste hard foam polyurethane plastic crushing, prepares porous plastics finished product.
Summary of the invention
An object of the present invention is used for by foamed polyurethane carrying out blending and modifying to monomer moulding casting nylon (MC nylon), significantly improves the toughness of monomer moulding casting nylon (MC nylon), thus provide a kind of foamed polyurethane modified MC nylon matrix material with this.
Two of object of the present invention is to provide a kind of preparation method of foamed polyurethane modified monomer nylon monomer-cast nylon (MC nylon) matrix material.
Foamed polyurethane modified MC nylon matrix material of the present invention after mixing, carries out polymerization by the raw material of following weight part to obtain, with the weight part of caprolactam monomer for benchmark, wherein:
Described foamed polyurethane powder be new foamed polyurethane or discarded foamed polyurethane through pulverizing as particle diameter is 5 ~ 1200 object foamed polyurethane powder, or the mixture of new foamed polyurethane and the foamed polyurethane discarded is through pulverizing as particle diameter is 5 ~ 1200 object foamed polyurethane powder.
Described basic catalyst is selected from one or more in sodium hydroxide, potassium hydroxide, magnesium hydroxide, sodium ethylate and potassium ethylate.
Described activator is selected from one or more in benzene 2,4-vulcabond (TDI), hexamethylene diisocyanate (HDI), '-diphenylmethane diisocyanate (MDI), poly methylene poly phenyl poly isocyanate (PAPI), triphenylmethane triisocyanate (JQ-1 glue) and diphenyl carbonate.
The preparation method of foamed polyurethane modified MC nylon matrix material of the present invention: with the weight part of caprolactam monomer for benchmark, the foamed polyurethane powder of the caprolactam monomer of 100 weight parts and 0.5 ~ 20 weight part is joined in container, vacuumize at temperature is 110 ~ 120 DEG C, dewater under vacuum conditions, during the pressure <500Pa of the system shown in gauge, add the basic catalyst of 0.005 ~ 0.5 weight part, continue to vacuumize, when temperature rises to 130 ~ 140 DEG C, system viscosity increases to the casting limit, remove vacuum, add the activator of 0.01 ~ 1 weight part, then be cast to rapidly in the mould of preheating (temperature is generally 160 ~ 200 DEG C), insulation (time of general insulation is 10 ~ 90 minutes) naturally cooling afterwards, the demoulding, namely the MC nylon composite materials of foamed polyurethane modification is obtained.
In the MC nylon composite materials of foamed polyurethane modification of the present invention, due to urethane (PU) and the generation of MC nylon copolymer, effectively improve the interface cohesion effect of two-phase, a small amount of PU just obviously can increase the resistance to impact shock of matrix material, toughness significantly improves, the requirements at the higher level of some industrial circle to material can be met, can better realize moulding Dai Gang, economizing on resources and reduce costs; For novel MC nylon composite materials is opened vast vistas.
Accompanying drawing explanation
Fig. 1. preparation technology's schematic flow sheet of foamed polyurethane modified MC nylon matrix material of the present invention.
Embodiment
Embodiment 1
By 400g caprolactam monomer and after new foamed polyurethane is pulverized the particle diameter that obtains be that 5 ~ 1200 object 2g foamed polyurethane powder join in the there-necked flask of 500ml, heating, after the complete melting of caprolactam monomer, vacuumize at temperature is 110 ~ 120 DEG C, dewater under vacuum conditions, occur when there being air pocket and the pressure <500Pa of system shown in vacuumometer time, add the NaOH of 0.6g, continue to vacuumize, when temperature to 130 ~ 140 DEG C, to again occurring air pocket and system viscosity increases to the casting limit (generally add NaOH after 20 minutes), remove vacuum, add the TDI of 0.2g, several lower there-necked flask of quick shake, then casting has been preheating in the mould of 170 DEG C rapidly, be incubated 30 minutes, naturally cool to non-scald on hand, the demoulding, namely the mass content obtaining PU is the MC nylon composite materials of the foamed polyurethane modification of 0.5%.
The MC nylon composite materials of foamed polyurethane modification obtained above is boiled 4 hours in the water-bath of 80 DEG C, to remove unpolymerized caprolactam monomer and oligopolymer, is then positioned in baking oven in 100 DEG C of dryings 8 hours.By through above-mentioned process and the MC nylon composite materials of dried foamed polyurethane modification take out and make bar samples, it is 20 DEG C in temperature, humidity be 50% thermostat container in the bar samples of the MC nylon composite materials of foamed polyurethane modification is placed 48 hours after, carry out performance test, the results are shown in Table 1.
Embodiment 2
Substantially identical with embodiment 1, just the new foamed polyurethane powder of 2g in embodiment 1 is made into the discarded foamed polyurethane powder of 8g, and the NaOH of 0.6g is made into the sodium ethylate of 0.8g, the mould of 170 DEG C makes the mould of 200 DEG C into, be incubated and within 30 minutes, make insulation 10 minutes into, other condition is constant, and the mass content of obtained PU is the MC nylon composite materials of the foamed polyurethane modification of 2%.The MC nylon composite materials of the foamed polyurethane modification obtained is carried out performance test, the results are shown in Table 1.
Embodiment 3
Substantially identical with embodiment 1, just make the foamed polyurethane powder of 2g in embodiment 1 the foamed polyurethane powder of 40g into, and the TDI of 0.2g is made into the MDI of 0.4g, be incubated and within 30 minutes, make insulation 60 minutes into, other condition is constant, and the mass content of obtained PU is the MC nylon composite materials of the foamed polyurethane modification of 10%.The MC nylon composite materials of the foamed polyurethane modification obtained is carried out performance test, the results are shown in Table 1.
Embodiment 4
Substantially identical with embodiment 1, just make the foamed polyurethane powder of 2g in embodiment 1 the foamed polyurethane powder of 80g into, and the TDI of 0.2g is made into the MDI of 0.8g, the mould of 170 DEG C makes the mould of 160 DEG C into, be incubated and within 30 minutes, make insulation 90 minutes into, other condition is constant, and the mass content of obtained PU is the MC nylon composite materials of the foamed polyurethane modification of 20%.The MC nylon composite materials of the foamed polyurethane modification obtained is carried out performance test, the results are shown in Table 1.
Comparative example 1
400g caprolactam monomer is joined in the there-necked flask (or two mouthfuls of bottles) of 500ml, with heating mantle heats, after the complete melting of caprolactam monomer, vacuumize at temperature is 110 ~ 120 DEG C, dewater under vacuum conditions, occur when there being air pocket and the pressure <500Pa of system shown in vacuumometer time, add the NaOH of 0.6g, continue to vacuumize, when temperature to 130 ~ 140 DEG C, to again occurring air pocket and the pressure <500Pa of system shown by vacuumometer, maintain 10 ~ 15 minutes, remove vacuum, add the TDI of 1.3ml, several lower there-necked flask of quick shake (or two mouthfuls of bottles), then casting has been preheating in the mould of 170 DEG C rapidly, be incubated 30 minutes, naturally cool to non-scald on hand, the demoulding, namely MC nylon is obtained.
MC nylon obtained above is boiled 4 hours in the water-bath of 80 DEG C, to remove unpolymerized caprolactam monomer and oligopolymer, is then positioned in baking oven in 100 DEG C of dryings 8 hours.Will through above-mentioned process and dried MC nylon take out and make bar samples, be 20 DEG C in temperature, humidity be 50% thermostat container in the bar samples of MC nylon is placed 48 hours after, carry out performance test, the results are shown in Table 1.
Table 1
Claims (1)
1. the preparation method of a foamed polyurethane modified MC nylon matrix material, it is characterized in that: with the weight part of caprolactam monomer for benchmark, the foamed polyurethane powder of the caprolactam monomer of 100 weight parts and 0.5 ~ 20 weight part is joined in container, vacuumize at temperature is 110 ~ 120 DEG C, dewater under vacuum conditions, during the pressure <500Pa of the system shown in gauge, add the basic catalyst of 0.005 ~ 0.5 weight part, continue to vacuumize, when temperature rises to 130 ~ 140 DEG C, remove vacuum, add the activator of 0.01 ~ 1 weight part, then be cast in the mould of preheating, naturally cooling after insulation, the demoulding, obtain the MC nylon composite materials of foamed polyurethane modification,
Described foamed polyurethane powder be new foamed polyurethane or discarded foamed polyurethane through pulverizing as particle diameter is 5 ~ 1200 object foamed polyurethane powder, or the mixture of new foamed polyurethane and the foamed polyurethane discarded is through pulverizing as particle diameter is 5 ~ 1200 object foamed polyurethane powder;
Described basic catalyst is selected from one or more in sodium hydroxide, potassium hydroxide, magnesium hydroxide, sodium ethylate and potassium ethylate;
Described activator is selected from one or more in benzene 2,4-vulcabond, hexamethylene diisocyanate, '-diphenylmethane diisocyanate, poly methylene poly phenyl poly isocyanate, triphenylmethane triisocyanate and diphenyl carbonate;
Described is cast in the mould of preheating, and wherein, the temperature of the mould of preheating is 160 ~ 200 DEG C;
The time of described insulation is 10 ~ 90 minutes.
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| CN201310642699.7A CN103834163B (en) | 2013-12-03 | 2013-12-03 | Foamed polyurethane modified MC nylon matrix material and preparation method thereof |
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| CN201310642699.7A CN103834163B (en) | 2013-12-03 | 2013-12-03 | Foamed polyurethane modified MC nylon matrix material and preparation method thereof |
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| CN103834163B true CN103834163B (en) | 2015-09-09 |
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| CN110105752A (en) * | 2019-03-20 | 2019-08-09 | 广东龙道新材料有限公司 | A kind of foaming modifying nylon composite materials and preparation method thereof |
| CN112175160A (en) * | 2020-10-14 | 2021-01-05 | 安徽宏翔农业机械有限公司 | Preparation method of high-strength clean agricultural ground roller adhesive |
| CN115654029B (en) * | 2022-10-31 | 2024-01-23 | 泰尔重工股份有限公司 | Universal coupling end face tooth, manufacturing method thereof and universal coupling |
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| CN100404586C (en) * | 2006-04-30 | 2008-07-23 | 华侨大学 | Process of anion in-situ preparation of thermoplastic polyurethane and MC nylon 6 composite materials |
| CN100404587C (en) * | 2006-04-30 | 2008-07-23 | 华侨大学 | Process of in-situ polycondensation preparation of thermoplastic polyurethane and nylon 6 composite materials |
| CN103232595A (en) * | 2012-04-16 | 2013-08-07 | 齐齐哈尔北坤合成高分子材料有限公司 | Modified MC nylon |
| CN102690413A (en) * | 2012-06-18 | 2012-09-26 | 河南省科学院高新技术研究中心 | Polyurethane modified nylon ball mill liner |
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Address after: 521031 8 East Road, Chang Mei melon garden, Fengxi District, Chaozhou, Guangdong Co-patentee after: Institute of Chemistry, Chinese Academy of Sciences Patentee after: Guangdong cojin new materials Co., Ltd. Address before: 521031 8 East Road, Chang Mei melon garden, Fengxi District, Chaozhou, Guangdong Co-patentee before: Institute of Chemistry, Chinese Academy of Sciences Patentee before: Guangdong Kejin Nylon Piping Product Co.ltd |