CN103910877B - A kind of transparent polyamide and preparation method thereof - Google Patents

A kind of transparent polyamide and preparation method thereof Download PDF

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CN103910877B
CN103910877B CN201210592812.0A CN201210592812A CN103910877B CN 103910877 B CN103910877 B CN 103910877B CN 201210592812 A CN201210592812 A CN 201210592812A CN 103910877 B CN103910877 B CN 103910877B
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reactor
temperature
transparent polyamide
acid
nylon
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CN103910877A (en
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马永梅
彭中樑
曹新宇
赵斌
贺丹
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Institute of Chemistry CAS
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Institute of Chemistry CAS
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Abstract

The present invention relates to transparent polyamide and preparation method thereof. The present invention is the feature of utilizing on the method for copolyreaction and aliphatic diacid monomer and alicyclic diamine monomer structure, by aliphatic diacid and alicyclic diamine and amidic-salt are carried out to copolyreaction, prepare a kind of light transmission rate in visible wavelength range and can reach more than 80% transparent polyamide material. Because this transparent polyamide material crystalline rate in preparation process is slow, grain growth difficulty, has finally formed the transparent polyamide material with microstructure feature. Because the crystallite dimension that forms the crystalline portion in this transparent polyamide material with microstructure feature is less than visible wavelength, thereby this material has the transparency. Meanwhile, this transparent polyamide material with microstructure still has higher degree of crystallinity, can keep higher mechanical strength.

Description

A kind of transparent polyamide and preparation method thereof
Technical field
The invention belongs to preparation and the production field of polyamide and polyamide copolymer, particularly thoroughly a kind ofBright polyamide and preparation method thereof.
Background technology
Polyamide is as a member in macromolecular material big family, and exploitation the earliest, most widely used, and demandMany, to study the most ripely, it prepares synthetic method and related physical chemical property in many documents and patentIn all have report. It is high that polyamide has intensity, Heat stability is good, and resistance to environment etc. are advantage better, makes itIn automobile, electronic apparatus, industrial machinery, weaving, the consumer goods and some other industry, obtain extensivelyApplication.
Conventionally by material, the light transmission rate in visible wavelength range (390nm~770nm) reaches 80%When above, be defined as and there is the transparency. Transparent polyamide has the poly-of property and purposes as a classAcid amides, is more and more paid attention to and is studied. European patent EP 50742, US Patent No.2696482, US2512606 and German patent DE 1595354, DE3717928 etc. have described multipleThe preparation method of bright polyamide. Find by above report, make polyamide macromolecular material have transparentProperty, first on selecting, raw material should guarantee that it is rendered as water white transparency state under melting condition, thenChange or suppress the crystallization process of polymer by correlation technique, when polymer is non-crystallizable or can only formWhen crystallite (crystallite dimension is less than visible wavelength), its scattering process to visible ray is very little, thereby canSee that light can see through material, material is shown as the transparency. Amorphous polymer often mechanical strength is lower,And the polymer with high-crystallinity microstructure has good mechanical strength and solvent resistance. For terribleTo this transparent polyamide material with microstructure, on selecting, monomer often needs to add long-chain fatFat family diacid and alicyclic diamine are as reaction raw materials. Wherein, the introducing of circulus, makes polymerThe space stereoregularity of strand reduces, and has weakened the hydrogen bond action between strand, causes polymerizationThing crystallization process imperfection, finally can only form the crystallite that crystallite dimension is less than visible wavelength.
Traditional polyamide has ensured it as its higher degree of crystallinity of nylon 66, NYLON610 and nylon 612Mechanical strength, but because crystallization process very easily forms spherocrystal, and spherocrystal diameter is greater than visible wavelength,Cause this polyamide not possess the transparency, the present invention is by institute in the preparation process of introducing transparent polyamideThe related raw material needing, distinguishes with amidic-salt it as nylon salt, NYLON610 salt and nylon 612 saltCarry out copolyreaction, the synthetic a kind of novel transparent polyamide of preparation, makes product have high strength, heightWhen degree of crystallinity advantage, there is again transparent feature. Selected related raw material in preparation process,Little to harm, be beneficial to and reclaim and deposit, the transparent polyamide obtaining, is a kind of functional form polyamide.
Summary of the invention
One of object of the present invention is to provide a kind of transparent polyamide material.
Two of object of the present invention is by by amidic-salt and aliphatic diacid monomer and alicyclic diamine monomerCarry out copolyreaction, thereby a kind of preparation method of transparent polyamide material is provided.
The present invention is the method for utilizing copolyreaction, and utilizes aliphatic diacid monomer and alicyclic diamine listFeature on body structure, by by very little toxic, hardly can be to the aliphatic of environment twoAcid and alicyclic diamine and amidic-salt carry out copolyreaction, have prepared a kind of at visible wavelength rangeLight transmission rate in (390nm~770nm) can reach more than 80% transparent polyamide material. By adjustingSave the component content of alicyclic diamine monomer, can control the external appearance characteristic of product, obtaining transparent polyamidesWhen amine material, also have traditional polyamide concurrently as some of nylon 66, NYLON610, nylon 612Good performance. Tradition polyamide as nylon 66, NYLON610, nylon 612 be very easily crystallization of a classMaterial, this makes these polyamide have higher intensity, but because crystallite dimension is larger, makes visibleLight cannot see through. Transparent polyamide material of the present invention crystalline rate in preparation process is slow, and crystal grain is rawLong difficulty, the crystallite dimension that the crystalline portion in transparent polyamide material forms is less than visible wavelength, forMicrostructure, therefore this material has the transparency. Meanwhile, there is the transparent poly-of microstructure due to thisAcid amides material still has higher degree of crystallinity, makes material can keep the advantage in these polyamide performances,Especially not significant reduction of hot strength. In addition, selected aliphatic diacid monomer and alicyclic twoAmine monomers, little to human body murder by poisoning, thus can be to environment, cost is moderate, and what obtain is transparentPolyamide belongs to environmental friendliness shaped material.
Transparent polyamide of the present invention is to be obtained after mixed melting polymerization by the raw material of following weight portion,Taking the weight portion of amidic-salt as benchmark, wherein:
Crystalline portion in described transparent polyamide is the crystal grain structure that is less than visible wavelength by crystallite dimensionBecome (light transmission rate in visible wavelength range (390nm~770nm) can reach more than 80%).
Described amidic-salt is selected from one or more in nylon salt, NYLON610 salt and nylon 612 salt.
Described aliphatic diacid select oneself diacid, pimelic acid, suberic acid, azelaic acid, SA, tenOne or more in one carbon diacid and dodecanedioic acid.
Described alicyclic diamine is selected from 4,4 '-diaminourea-dicyclohexyl methyl hydride, 4,4 '-diaminourea-dicyclohexylPropane, 3,3 '-dimethyl-4, the one in 4 '-diaminourea-dicyclohexyl methyl hydride and IPD or severalKind.
Described molecular weight fine setting agent is selected from the one in benzoic acid and acetic acid.
Described catalyst is selected from the one in ortho phosphorous acid and N-acetyl group caprolactam.
The described molecular weight regulator one in diacid and dodecanedioic acid of selecting oneself.
Described solvent is selected from the one in deionized water, 1-METHYLPYRROLIDONE and metacresol.
The preparation method of transparent polyamide of the present invention comprises the following steps, taking the weight portion of amidic-salt as baseAccurate:
(1) solvent of 100~400 weight portions is joined in reactor, open agitator, by 100 weightsThe amidic-salt of amount part, the molecular weight regulator of 5~30 weight portions, the aliphatic diacid of 25~100 weight portionsJoin in solvent with the alicyclic diamine of 25~100 weight portions, after being uniformly mixed, to reactorIn add the molecular weight fine setting agent of 0.01~1 weight portion and the catalyst of 0.02~0.5 weight portion, continue to stirMix, until above all raw materials mix;
(2) reactor of airtight step (1), carries out inflated with nitrogen and vacuumizes processing to discharge to reactorAir in reactor; Then in reactor, be filled with nitrogen, the initial pressure in reactor is maintainedBetween 0.2~0.5MPa;
(3) temperature that the initial pressure of step (2) is maintained to the reactor between 0.2~0.5MPa byIt is 180~230 DEG C that room temperature was evenly warming up to temperature in 60~120 minutes, and is incubated 30~90 minutes,Pressure in reactor is maintained between 1.5~2MPa simultaneously; Then continue heating reactor, makeThe temperature of reactor was 180~220 DEG C by temperature and is warming up to temperature and is 260 in 90~180 minutes~300 DEG C, during this period, at the uniform velocity reduce pressure in reactor to normal pressure, and get rid of the gas in reactorMaterial; Be 260~300 DEG C of insulations after 30~60 minutes in temperature, open vavuum pump, by reactorPressure drop is low to moderate 0.1~0.003mbar, and continues 1~4 hour under this pressure; Stop stirring, to insteadAnswer in still and be filled with nitrogen, make the pressure in reactor be increased to 0.2~0.5MPa by 0.1~0.003mbar,Open the outlet valve of reactor, the water white transparency melt of outflow obtains transparent polyamide after ice-water bath quenches.
Crystalline portion in described transparent polyamide is the crystal grain structure that is less than visible wavelength by crystallite dimensionBecome (light transmission rate in visible wavelength range (390nm~770nm) can reach more than 80%).
The present invention has following features:
(1) transparent polyamide that prepared by the present invention, crystallite dimension is small, and outward appearance has the transparency.
(2) transparent polyamide that prepared by the present invention, degree of crystallinity is higher, have traditional polyamide as nylon 66,The feature of the high tensile of NYLON610, nylon 612.
(3) transparent polyamide that prepared by the present invention can be with other additive as thermo oxidative aging agent, fire retardant,The effectively blend such as colouring agent.
(4) transparent polyamide that prepared by the present invention, selected aliphatic diacid, alicyclic diamine and acylAmine salt, raw material obtains easily, and moderate cost is nontoxic to environment, and the transparent polyamide obtaining is onePlant function polyamide.
Detailed description of the invention
Embodiment 1
(1) 1000g deionized water is joined in reactor, open agitator, by 300g nylon 66Salt, 22g adipic acid, 120g dodecanedioic acid, 120g4,4 '-diaminourea-dicyclohexyl-methane, joinsIn deionized water; After raw material is uniformly mixed, to adding 0.5g benzoic acid and 0.1g time in reactorPhosphorous acid, continues to stir, until above all raw materials mix;
(2) reactor of airtight step (1), carries out inflated with nitrogen and vacuumizes processing 3~5 to reactorInferior to discharge the air in reactor; Then in reactor, be filled with nitrogen, make the initial pressure in reactorMaintain by force between 0.2MPa;
(3) open heater, the initial pressure of step (2) is maintained to the reactor of 0.2MPaTemperature was evenly warming up to temperature in 90 minutes by room temperature be 180 DEG C, and be incubated 30 minutes, simultaneously will be anti-Answer the pressure in still to maintain between 1.5MPa; Then continue heating reactor, make the temperature of reactorIn 120 minutes, being 180 DEG C by temperature, to be warming up to temperature be 280 DEG C, during this period, at the uniform velocity reduces reactionPressure in still is to normal pressure, and gets rid of the gaseous matter in reactor; Be 30 points of 280 DEG C of insulations in temperatureZhong Hou, opens vavuum pump, and the pressure drop in reactor is low to moderate to 0.003mbar, and continues under this pressure1 hour; Stop stirring, in reactor, be filled with nitrogen, make pressure in reactor by 0.003mbar literHeight, to 0.2MPa, is opened the outlet valve of reactor, and water white transparency nylon 66 melts of outflow are through ice-water bathAfter quenching, obtain transparent nylon 66. Gained transparent nylon 66(crystalline portion is to be less than from crystallite dimensionThe crystal grain of optical wavelength forms) light transmission rate in visible wavelength range (390nm~770nm) is 80%Above.
The transparent nylon 66 preparing is water white transparency homogeneous melt in the time that temperature is 280 DEG C, after quenchingFor colourless transparent material. With the LIV-1601PC ultraviolet-uisible spectrophotometer test of Japanese Shimadzu company thoroughlyThe uv transmittance of bright nylon 66, the DXL-10000 stretching-machine by capital science and technology condition platform is to itMechanical strength characterizes, and the results are shown in Table 1.
Table 1
Embodiment 2
(1) 1000g deionized water is joined in reactor, open agitator, by 270g nylon 66Salt, 20g adipic acid, 139g dodecanedioic acid, 139g4,4 '-diaminourea-dicyclohexyl-methane, joinsIn deionized water; After raw material is uniformly mixed, in reactor, add 0.3g benzoic acid and 0.08gOrtho phosphorous acid, continues to stir, until above all raw materials mix;
(2) reactor of airtight step (1), carries out inflated with nitrogen and vacuumizes processing 3~5 to reactorInferior to discharge the air in reactor; Then in reactor, be filled with nitrogen, make the initial pressure in reactorMaintain by force between 0.5MPa;
(3) open heater, the initial pressure of step (2) is maintained to the reactor of 0.5MPaTemperature was evenly warming up to temperature in 120 minutes by room temperature be 220 DEG C, and be incubated 60 minutes, will simultaneouslyPressure in reactor maintains between 2MPa; Then continue heating reactor, make the temperature of reactorIn 180 minutes, being 220 DEG C by temperature, to be warming up to temperature be 285 DEG C, during this period, at the uniform velocity reduces reactionPressure in still is to normal pressure, and gets rid of the gaseous matter in reactor; Be 60 points of 285 DEG C of insulations in temperatureZhong Hou, opens vavuum pump, and the pressure drop in reactor is low to moderate to 0.003mbar, and continues under this pressure4 hours; Stop stirring, in reactor, be filled with nitrogen, make pressure in reactor by 0.003mbar literHeight, to 0.5MPa, is opened the outlet valve of reactor, and water white transparency nylon 66 melts of outflow are through ice-water bathAfter quenching, obtain transparent nylon 66. Gained transparent nylon 66(crystalline portion is to be less than from crystallite dimensionThe crystal grain of optical wavelength forms) light transmission rate in visible wavelength range (390nm~770nm) is 80%Above.
The transparent nylon 66 preparing is water white transparency homogeneous melt in the time that temperature is 285 DEG C, after quenchingFor colourless transparent material. With the LIV-1601PC ultraviolet-uisible spectrophotometer test of Japanese Shimadzu company thoroughlyThe uv transmittance of bright nylon 66, the DXL-10000 stretching-machine by capital science and technology condition platform is to itMechanical strength characterizes, and the results are shown in Table 2.
Table 2
Embodiment 3
(1) 1000g deionized water is joined in reactor, open agitator, by 300g nylon 66Salt, 22g adipic acid, 100g dodecanedioic acid, 100g4,4 '-diaminourea-dicyclohexyl-methane, joinsIn deionized water; After raw material is uniformly mixed, to adding 0.5g benzoic acid and 0.1g time in reactorPhosphorous acid, continues to stir, until above all raw materials mix;
(2) reactor of airtight step (1), carries out inflated with nitrogen and vacuumizes processing 3~5 to reactorInferior to discharge the air in reactor; Then in reactor, be filled with nitrogen, make the initial pressure in reactorMaintain by force between 0.5MPa;
(3) open heater, the initial pressure of step (2) is maintained to the reactor of 0.5MPaTemperature was evenly warming up to temperature in 100 minutes by room temperature be 200 DEG C, and be incubated 50 minutes, will simultaneouslyPressure in reactor maintains between 1.5MPa; Then continue heating reactor, make the temperature of reactorDegree was 200 DEG C by temperature in 120 minutes, and to be warming up to temperature be 280 DEG C, during this period, at the uniform velocity reduces anti-Answer pressure in still to normal pressure, and get rid of the gaseous matter in reactor; Be 280 DEG C of insulations 30 in temperatureAfter minute, open vavuum pump, the pressure drop in reactor is low to moderate to 0.003mbar, and hold under this pressureContinuous 2 hours; Stop stirring, in reactor, be filled with nitrogen, make pressure in reactor by 0.003mbarBe increased to 0.5MPa, open the outlet valve of reactor, water white transparency nylon 66 melts of outflow are through frozen waterAfter bathing quenching, obtain transparent nylon 66. Gained transparent nylon 66(crystalline portion is that be less than by crystallite dimension canThe crystal grain of seeing optical wavelength forms) light transmission rate in visible wavelength range (390nm~770nm) existsMore than 80%.
The transparent nylon 66 preparing is water white transparency homogeneous melt in the time that temperature is 280 DEG C, after quenchingFor colourless transparent material. With the LIV-1601PC ultraviolet-uisible spectrophotometer test of Japanese Shimadzu company thoroughlyThe uv transmittance of bright nylon 66, the DXL-10000 stretching-machine by capital science and technology condition platform is to itMechanical strength characterizes, and the results are shown in Table 3.
Table 3
Embodiment 4
(1) 1000g deionized water is joined in reactor, open agitator, by 305g nylon 66Salt, 22g adipic acid, 102g dodecanedioic acid, 108g3,3 '-dimethyl-4,4 '-diaminourea-dicyclohexyl firstAlkane, joins in deionized water; After raw material is uniformly mixed, in reactor, add 0.5g benzene firstAcid and 0.1g ortho phosphorous acid, continue to stir, until above all raw materials mix;
(2) reactor of airtight step (1), carries out inflated with nitrogen and vacuumizes processing 3~5 to reactorInferior to discharge the air in reactor; Then in reactor, be filled with nitrogen, make the initial pressure in reactorMaintain by force between 0.5MPa;
(3) open heater, the initial pressure of step (2) is maintained to the reactor of 0.5MPaTemperature was evenly warming up to temperature in 120 minutes by room temperature be 180 DEG C, and be incubated 30 minutes, will simultaneouslyPressure in reactor maintains between 1.5MPa; Then continue heating reactor, make the temperature of reactorDegree was 180 DEG C by temperature in 120 minutes, and to be warming up to temperature be 280 DEG C, during this period, at the uniform velocity reduces anti-Answer pressure in still to normal pressure, and get rid of the gaseous matter in reactor; Be 280 DEG C of insulations 30 in temperatureAfter minute, open vavuum pump, the pressure drop in reactor is low to moderate to 0.003mbar, and hold under this pressureContinuous 1 hour; Stop stirring, in reactor, be filled with nitrogen, make pressure in reactor by 0.003mbarBe increased to 0.2~0.5MPa, open the outlet valve of reactor, the water white transparency nylon 66 melt warps of outflowIce-water bath obtains transparent nylon 66 after quenching. Gained transparent nylon 66(crystalline portion is little by crystallite dimensionForm in the crystal grain of visible wavelength) light transmission in visible wavelength range (390nm~770nm)Rate is more than 80%.
The transparent nylon 66 preparing is water white transparency homogeneous melt in the time that temperature is 280 DEG C, after quenchingFor colourless transparent material. With the LIV-1601PC ultraviolet-uisible spectrophotometer test of Japanese Shimadzu company thoroughlyThe uv transmittance of bright nylon 66, the DXL-10000 stretching-machine by capital science and technology condition platform is to itMechanical strength characterizes, and the results are shown in Table 4.
Table 4
Embodiment 5
(1) 1000g metacresol joins in reactor, opens agitator, by 305g nylon salt, 22gAdipic acid, 102g dodecanedioic acid, 108g3,3 '-dimethyl-4,4 '-diaminourea-dicyclohexyl methyl hydride, addsEnter in metacresol; After raw material is uniformly mixed, in reactor, add 0.5g benzoic acid and 0.1gOrtho phosphorous acid, continues to stir, until above all raw materials mix;
(2) reactor of airtight step (1), carries out inflated with nitrogen and vacuumizes processing 3~5 to reactorInferior to discharge the air in reactor; Then in reactor, be filled with nitrogen, make the initial pressure in reactorMaintain by force between 0.5MPa;
(3) open heater, the initial pressure of step (2) is maintained to the reactor of 0.5MPaTemperature was evenly warming up to temperature in 90 minutes by room temperature be 180 DEG C, and be incubated 30 minutes, simultaneously will be anti-Answer the pressure in still to maintain between 1.5MPa; Then continue heating reactor, make the temperature of reactorIn 120 minutes, being 180 DEG C by temperature, to be warming up to temperature be 280 DEG C, during this period, at the uniform velocity reduces reactionPressure in still is to normal pressure, and gets rid of the gaseous matter in reactor; Be 30 points of 280 DEG C of insulations in temperatureZhong Hou, opens vavuum pump, and the pressure drop in reactor is low to moderate to 0.003mbar, and continues under this pressure1 hour; Stop stirring, in reactor, be filled with nitrogen, make pressure in reactor by 0.003mbar literHeight, to 0.2MPa, is opened the outlet valve of reactor, and water white transparency nylon 66 melts of outflow are through ice-water bathAfter quenching, obtain transparent nylon 66. Gained transparent nylon 66(crystalline portion is to be less than from crystallite dimensionThe crystal grain of optical wavelength forms) light transmission rate in visible wavelength range (390nm~770nm) is 80%Above.
The transparent nylon 66 preparing is water white transparency homogeneous melt in the time that temperature is 280 DEG C, after quenchingFor colourless transparent material. With the LIV-1601PC ultraviolet-uisible spectrophotometer test of Japanese Shimadzu company thoroughlyThe uv transmittance of bright nylon 66, the DXL-10000 stretching-machine by capital science and technology condition platform is to itMechanical strength characterizes, and the results are shown in Table 5.
Table 5
Embodiment 6
(1) 1000g deionized water is joined in reactor, open agitator, by 280g nylon 66Salt, 15g is 12 carbon two as aliphatic diacid as the dodecanedioic acid of molecular weight regulator, 121gAcid, 121g IPD, join in deionized water; After raw material is uniformly mixed, to insteadAnswer in still and add 0.5g benzoic acid and 0.1g ortho phosphorous acid, continue to stir, until above all raw materials mixEvenly;
(2) reactor of airtight step (1), carries out inflated with nitrogen and vacuumizes processing 3~5 to reactorInferior to discharge the air in reactor; Then in reactor, be filled with nitrogen, make the initial pressure in reactorMaintain by force between 0.5MPa;
(3) open heater, the initial pressure of step (2) is maintained to the reactor of 0.5MPaTemperature was evenly warming up to temperature in 90 minutes by room temperature be 180 DEG C, and be incubated 30 minutes, simultaneously will be anti-Answer the pressure in still to maintain between 1.5MPa; Then continue heating reactor, make the temperature of reactorIn 120 minutes, being 180 DEG C by temperature, to be warming up to temperature be 280 DEG C, during this period, at the uniform velocity reduces reactionPressure in still is to normal pressure, and gets rid of the gaseous matter in reactor; Be 30 points of 280 DEG C of insulations in temperatureZhong Hou, opens vavuum pump, and the pressure drop in reactor is low to moderate to 0.003mbar, and continues under this pressure1 hour; Stop stirring, in reactor, be filled with nitrogen, make pressure in reactor by 0.003mbar literHeight, to 0.2MPa, is opened the outlet valve of reactor, and water white transparency nylon 66 melts of outflow are through ice-water bathAfter quenching, obtain transparent nylon 66. Gained transparent nylon 66(crystalline portion is to be less than from crystallite dimensionThe crystal grain of optical wavelength forms) light transmission rate in visible wavelength range (390nm~770nm) is 80%Above.
The transparent nylon 66 preparing is water white transparency homogeneous melt in the time that temperature is 280 DEG C, after quenchingFor colourless transparent material.
Embodiment 7
(1) 1000gN-methyl pyrrolidone is joined in reactor, open agitator, by 270g Buddhist nunDragon 66 salt, 20g as the adipic acid of molecular weight regulator, 138g as the adipic acid of aliphatic diacid,159g4,4 '-diaminourea-dicyclohexyl-methane, joins in 1-METHYLPYRROLIDONE; When raw material stirs mixedAfter closing evenly, in reactor, add 0.3g benzoic acid and 0.08g ortho phosphorous acid, continue to stir, untilTill all raw materials mix above;
(2) reactor of airtight step (1), carries out inflated with nitrogen and vacuumizes processing 3~5 to reactorInferior to discharge the air in reactor; Then in reactor, be filled with nitrogen, make the initial pressure in reactorMaintain by force between 0.5MPa;
(3) open heater, the initial pressure of step (2) is maintained to the reactor of 0.5MPaTemperature was evenly warming up to temperature in 90 minutes by room temperature be 180 DEG C, and be incubated 30 minutes, simultaneously will be anti-Answer the pressure in still to maintain between 1.5MPa; Then continue heating reactor, make the temperature of reactorIn 120 minutes, being 180 DEG C by temperature, to be warming up to temperature be 280 DEG C, during this period, at the uniform velocity reduces reactionPressure in still is to normal pressure, and gets rid of the gaseous matter in reactor; Be 30 points of 280 DEG C of insulations in temperatureZhong Hou, opens vavuum pump, and the pressure drop in reactor is low to moderate to 0.003mbar, and continues under this pressure1 hour; Stop stirring, in reactor, be filled with nitrogen, make pressure in reactor by 0.003mbar literHeight, to 0.2MPa, is opened the outlet valve of reactor, and water white transparency nylon 66 melts of outflow are quenched through ice-water bathAfter fire, obtain transparent nylon 66. Gained transparent nylon 66(crystalline portion is to be less than visible ray by crystallite dimensionThe crystal grain of wavelength forms) light transmission rate in visible wavelength range (390nm~770nm) is 80%Above.
The transparent nylon 66 preparing is water white transparency homogeneous melt in the time that temperature is 280 DEG C, after quenchingFor colourless transparent material.
Embodiment 8
(1) 3000g deionized water is joined in reactor, open agitator, by 320g nylon 66Salt, 15g adipic acid, 75g 11 carbon diacid, 75g4,4 '-diaminourea-dicyclohexyl-methane, joinsIn ionized water; After raw material is uniformly mixed, to adding 0.03g benzoic acid and 0.06g time in reactorPhosphorous acid, continues to stir, until above all raw materials mix;
(2) reactor of airtight step (1), carries out inflated with nitrogen and vacuumizes processing 3~5 to reactorInferior to discharge the air in reactor; Then in reactor, be filled with nitrogen, make the initial pressure in reactorMaintain by force between 0.2MPa;
(3) open heater, the initial pressure of step (2) is maintained to the reactor of 0.2MPaTemperature was evenly warming up to temperature in 60 minutes by room temperature be 180 DEG C, and be incubated 30 minutes, simultaneously will be anti-Answer the pressure in still to maintain between 1.5MPa; Then continue heating reactor, make the temperature of reactorIn 90 minutes, being 180 DEG C by temperature, to be warming up to temperature be 260 DEG C, during this period, at the uniform velocity reduces reactionPressure in still is to normal pressure, and gets rid of the gaseous matter in reactor; Be 30 points of 260 DEG C of insulations in temperatureZhong Hou, opens vavuum pump, and the pressure drop in reactor is low to moderate to 0.1mbar, and continues 1 under this pressureHour; Stop stirring, in reactor, be filled with nitrogen, the pressure in reactor is increased to by 0.1mbar0.2MPa, opens the outlet valve of reactor, and water white transparency nylon 66 melts of outflow are after ice-water bath quenchesObtain transparent nylon 66. Gained transparent nylon 66(crystalline portion is to be less than visible wavelength by crystallite dimensionCrystal grain form) light transmission rate in visible wavelength range (390nm~770nm) is more than 80%.
The transparent nylon 66 preparing is water white transparency homogeneous melt in the time that temperature is 280 DEG C, after quenchingFor colourless transparent material.
Embodiment 9
(1) 1200g deionized water is joined in reactor, open agitator, by 300g nylon 66Salt, 90g adipic acid, 300g SA, 300g4,4 '-diaminourea-dicyclohexyl-methane, join fromIn sub-water; After raw material is uniformly mixed, in reactor, add 3g benzoic acid and 1.5g ortho phosphorous acid,Continue to stir, until above all raw materials mix;
(2) reactor of airtight step (1), carries out inflated with nitrogen and vacuumizes processing 3~5 to reactorInferior to discharge the air in reactor; Then in reactor, be filled with nitrogen, make the initial pressure in reactorMaintain by force between 0.5MPa;
(3) open heater, the initial pressure of step (2) is maintained to the reactor of 0.5MPaTemperature was evenly warming up to temperature in 120 minutes by room temperature be 230 DEG C, and be incubated 90 minutes, will simultaneouslyPressure in reactor maintains between 2MPa; Then continue heating reactor, make the temperature of reactorIn 180 minutes, being 220 DEG C by temperature, to be warming up to temperature be 300 DEG C, during this period, at the uniform velocity reduces reactionPressure in still is to normal pressure, and gets rid of the gaseous matter in reactor; Be 60 points of 300 DEG C of insulations in temperatureZhong Hou, opens vavuum pump, and the pressure drop in reactor is low to moderate to 0.003mbar, and continues under this pressure4 hours; Stop stirring, in reactor, be filled with nitrogen, make pressure in reactor by 0.003mbar literHeight, to 0.5MPa, is opened the outlet valve of reactor, and water white transparency nylon 66 melts of outflow are through ice-water bathAfter quenching, obtain transparent nylon 66. Gained transparent nylon 66(crystalline portion is to be less than from crystallite dimensionThe crystal grain of optical wavelength forms) light transmission rate in visible wavelength range (390nm~770nm) is 80%Above.
The transparent nylon 66 preparing is water white transparency homogeneous melt in the time that temperature is 280 DEG C, after quenchingFor colourless transparent material.
Embodiment 10
(1) 1000g deionized water is joined in reactor, open agitator, by 290g nylon 66Salt, 70g adipic acid, 74g suberic acid and 74g azelaic acid, 111g4,4 '-diaminourea-dicyclohexyl propaneAnd 111g3,3 '-dimethyl-4,4 '-diaminourea-dicyclohexyl methyl hydride, joins in deionized water; Work as raw materialAfter being uniformly mixed, in reactor, add 0.8g benzoic acid and 0.3g ortho phosphorous acid, continue to stir,Until above all raw materials mix;
(2) reactor of airtight step (1), carries out inflated with nitrogen and vacuumizes processing 3~5 to reactorInferior to discharge the air in reactor; Then in reactor, be filled with nitrogen, make the initial pressure in reactorMaintain by force between 0.2MPa;
(3) open heater, the initial pressure of step (2) is maintained to the reactor of 0.2MPaTemperature was evenly warming up to temperature in 90 minutes by room temperature be 180 DEG C, and be incubated 30 minutes, simultaneously will be anti-Answer the pressure in still to maintain between 1.5MPa; Then continue heating reactor, make the temperature of reactorIn 120 minutes, being 180 DEG C by temperature, to be warming up to temperature be 280 DEG C, during this period, at the uniform velocity reduces reactionPressure in still is to normal pressure, and gets rid of the gaseous matter in reactor; Be 30 points of 280 DEG C of insulations in temperatureZhong Hou, opens vavuum pump, and the pressure drop in reactor is low to moderate to 0.003mbar, and continues under this pressure1 hour; Stop stirring, in reactor, be filled with nitrogen, make pressure in reactor by 0.003mbar literHeight, to 0.2MPa, is opened the outlet valve of reactor, and water white transparency nylon 66 melts of outflow are through ice-water bathAfter quenching, obtain transparent nylon 66. Gained transparent nylon 66(crystalline portion is to be less than from crystallite dimensionThe crystal grain of optical wavelength forms) light transmission rate in visible wavelength range (390nm~770nm) is 80%Above.
The transparent nylon 66 preparing is water white transparency homogeneous melt in the time that temperature is 280 DEG C, after quenchingFor colourless transparent material.
Embodiment 11
(1) 1000g deionized water is joined in reactor, open agitator, by 300g NYLON610Salt, 16g adipic acid, 139g dodecanedioic acid, 139g4,4 '-diaminourea-dicyclohexyl-methane, joinsIn deionized water; After raw material is uniformly mixed, in reactor, add 0.2g benzoic acid and 0.05gOrtho phosphorous acid, continues to stir, until above all raw materials mix;
(2) reactor of airtight step (1), carries out inflated with nitrogen and vacuumizes processing 3~5 to reactorInferior to discharge the air in reactor; Then in reactor, be filled with nitrogen, make the initial pressure in reactorMaintain by force between 0.2MPa;
(3) open heater, the initial pressure of step (2) is maintained to the reactor of 0.2MPaTemperature was evenly warming up to temperature in 90 minutes by room temperature be 210 DEG C, and be incubated 30 minutes, simultaneously will be anti-Answer the pressure in still to maintain between 1.5MPa; Then continue heating reactor, make the temperature of reactorIn 120 minutes, being 210 DEG C by temperature, to be warming up to temperature be 290 DEG C, during this period, at the uniform velocity reduces reactionPressure in still is to normal pressure, and gets rid of the gaseous matter in reactor; Be 30 points of 290 DEG C of insulations in temperatureZhong Hou, opens vavuum pump, and the pressure drop in reactor is low to moderate to 0.1mbar, and continues 1 under this pressureHour; Stop stirring, in reactor, be filled with nitrogen, the pressure in reactor is increased to by 0.1mbar0.5MPa, opens the outlet valve of reactor, and the water white transparency NYLON610 melt of outflow quenches through ice-water bathAfter obtain transparent nylon 610. Gained transparent nylon 610(crystalline portion is to be less than visible ray by crystallite dimensionThe crystal grain of wavelength forms) light transmission rate in visible wavelength range (390nm~770nm) is 80%Above.
The transparent nylon 610 preparing is water white transparency homogeneous melt in the time that temperature is 290 DEG C, after quenchingFor colourless transparent material.
Embodiment 12
(1) 1000g deionized water is joined in reactor, open agitator, by 300g nylon 612Salt, 21g adipic acid, 128g dodecanedioic acid, 133g3,3 '-dimethyl-4,4 '-diaminourea-dicyclohexyl firstAlkane, joins in deionized water; After raw material is uniformly mixed, in reactor, add 0.2g benzene firstAcid and 0.05g ortho phosphorous acid, continue to stir, until above all raw materials mix;
(2) reactor of airtight step (1), carries out inflated with nitrogen and vacuumizes processing 3~5 to reactorInferior to discharge the air in reactor; Then in reactor, be filled with nitrogen, make the initial pressure in reactorMaintain by force between 0.2MPa;
(3) open heater, the initial pressure of step (2) is maintained to the reactor of 0.2MPaTemperature was evenly warming up to temperature in 90 minutes by room temperature be 180 DEG C, and be incubated 30 minutes, simultaneously will be anti-Answer the pressure in still to maintain between 1.5MPa; Then continue heating reactor, make the temperature of reactorIn 120 minutes, being 180 DEG C by temperature, to be warming up to temperature be 260 DEG C, during this period, at the uniform velocity reduces reactionPressure in still is to normal pressure, and gets rid of the gaseous matter in reactor; Be 30 points of 260 DEG C of insulations in temperatureZhong Hou, opens vavuum pump, and the pressure drop in reactor is low to moderate to 0.003mbar, and continues under this pressure1 hour; Stop stirring, in reactor, be filled with nitrogen, make pressure in reactor by 0.003mbar literHeight, to 0.2MPa, is opened the outlet valve of reactor, and the water white transparency nylon 612 melt of outflow is through ice-water bathAfter quenching, obtain transparent nylon 612. Gained transparent nylon 612(crystalline portion is that be less than by crystallite dimension canThe crystal grain of seeing optical wavelength forms) light transmission rate in visible wavelength range (390nm~770nm) existsMore than 80%.
The transparent nylon 612 preparing is water white transparency homogeneous melt in the time that temperature is 260 DEG C, after quenchingFor colourless transparent material.

Claims (6)

1. a transparent polyamide, it is to be obtained after mixed melting polymerization by the raw material of following weight portion,It is characterized in that, taking the weight portion of amidic-salt as benchmark:
Described amidic-salt is selected from one or more in nylon salt, NYLON610 salt and nylon 612 salt;
Described aliphatic diacid select oneself diacid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, tenOne or more in one carbon diacid and dodecanedioic acid;
Described alicyclic diamine is selected from 4,4 '-diaminourea-dicyclohexyl methyl hydride, 4,4 '-diaminourea-dicyclohexylPropane, 3,3 '-dimethyl-4, the one in 4 '-diaminourea-dicyclohexyl methyl hydride and IPD or severalKind;
Crystalline portion in described transparent polyamide is the crystal grain structure that is less than visible wavelength by crystallite dimensionBecome, the light transmission rate in visible wavelength range 390nm~770nm is more than 80%.
2. transparent polyamide according to claim 1, is characterized in that: described molecular weight fine setting agent choosingOne in benzoic acid and acetic acid.
3. transparent polyamide according to claim 1, is characterized in that: described catalyst is selected from time AsiaOne in phosphoric acid and N-acetyl group caprolactam.
4. transparent polyamide according to claim 1, is characterized in that: described molecular weight regulator choosingOne in adipic acid and dodecanedioic acid.
5. transparent polyamide according to claim 1, is characterized in that: described solvent is selected from deionizationOne in water, 1-METHYLPYRROLIDONE and metacresol.
6. according to a preparation method for the transparent polyamide described in claim 1~5 any one, its spyLevy and be, described preparation method comprises the following steps, taking the weight portion of amidic-salt as benchmark:
(1) solvent of 100~400 weight portions is joined in reactor, open agitator, by 100 weightsThe amidic-salt of amount part, the molecular weight regulator of 5~30 weight portions, the aliphatic diacid of 25~100 weight portionsJoin in solvent with the alicyclic diamine of 25~100 weight portions, after being uniformly mixed, to reactorIn add the molecular weight fine setting agent of 0.01~1 weight portion and the catalyst of 0.02~0.5 weight portion, continue to stirMix, until above all raw materials mix;
(2) reactor of airtight step (1), carries out inflated with nitrogen and vacuumizes processing to discharge to reactorAir in reactor; Then in reactor, be filled with nitrogen, the initial pressure in reactor is maintainedBetween 0.2~0.5MPa;
(3) temperature that the initial pressure of step (2) is maintained to the reactor between 0.2~0.5MPa byIt is 180~230 DEG C that room temperature was evenly warming up to temperature in 60~120 minutes, and is incubated 30~90 minutes,Pressure in reactor is maintained between 1.5~2MPa simultaneously; Then continue heating reactor, makeThe temperature of reactor was 180~220 DEG C by temperature and is warming up to temperature and is 260 in 90~180 minutes~300 DEG C, during this period, at the uniform velocity reduce pressure in reactor to normal pressure, and get rid of the gas in reactorMaterial; Be 260~300 DEG C of insulations after 30~90 minutes in temperature, open vavuum pump, by reactorPressure drop is low to moderate 0.003~0.1mbar, and continues 1~4 hour under this pressure; Stop stirring, to insteadAnswer in still and be filled with nitrogen, make the pressure in reactor be increased to 0.2~0.5MPa by 0.003~0.1mbar,Open the outlet valve of reactor, the water white transparency melt of outflow obtains transparent polyamide after cooling.
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