CN105860058A - PA6/PA66 binary copolymer material and preparation method thereof - Google Patents
PA6/PA66 binary copolymer material and preparation method thereof Download PDFInfo
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- CN105860058A CN105860058A CN201610263526.8A CN201610263526A CN105860058A CN 105860058 A CN105860058 A CN 105860058A CN 201610263526 A CN201610263526 A CN 201610263526A CN 105860058 A CN105860058 A CN 105860058A
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- 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
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
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Abstract
The invention relates to the technical field of nylon material preparation and particularly relates to a PA6/PA66 binary copolymer material and a preparation method thereof. The PA6/PA66 binary copolymer material is prepared by the following steps: melting and copolymerizing caprolactam and hexanediamine adipate in a mass ratio of (6-9) to (4-1); and grinding and screening to obtain the PA6/PA66 binary copolymer material. A product obtained by SLS processing of the PA6/PA66 binary copolymer material provided by the invention has the advantages of excellent performance, low sintering temperature, low cost and high repeated utilization rate; and moreover, the preparation technology is simple, the preparation cost is low, and the production is stable.
Description
Technical field
The present invention relates to nylon material preparing technical field, be specifically related to a kind of PA6/PA66 binary copolymerization material and system thereof
Preparation Method.
Background technology
Selective laser sintering (Selective Laser Sintering is called for short SLS) is that development in recent years is the rapidest
One of rapid shaping technique, it is with pressed powder as raw material, uses laser successively to scan through the cross section of 3D solid
Becoming raw basin, its manufactures is not limited by part shape complexity, can accurately fast restore design concept, quickly production is newly
The functional test part of product, small lot batch manufacture complex parts, breach the restriction of traditional manufacturing technology.
In theory, the powder of any crystallization or those semi-crystalline materials can serve as SLS sintered material, scope of selecting material
It it is extensively one of SLS technique key factor of can be widely applied for each field.Nylon is a kind of semi-crystalline polymer, its SLS system
Part all has more excellent performance at the aspect such as intensity, consistency, is a kind of macromolecule material being highly suitable for SLS technique
Material.
The nylon powder of the existing SLS of being applied to sintering is mainly PA12, PA11 and PA6 three major types.But apply in reality
In, the price of PA12PA11 costly, and its mechanical property than PA6 low by about one time.Although PA6 material has good mechanical property
Can, but its notch impact strength is poor, and fusing point is higher, and at about 230 DEG C, so that its burning in the SLS course of processing
Junction temperature need to be more than 200 DEG C, and when PA6 powder is chronically at 200 DEG C of high temperature above, its oxidation is very serious, can make powder
End turns yellow, and solution is to add pigment in the powder color to be covered, but the problem of part performance variation about 20% cannot obtain
To solving, and material oxidation flavescence influences whether reusing of powder, therefore current PA6 dusty material can not well be fitted
Sinter for SLS.
Summary of the invention
In order to overcome shortcoming and defect present in prior art, it is an object of the invention to provide a kind of PA6/PA66 bis-
Unit's copolymeric material, the part performance using this PA6/PA66 binary copolymerization material to obtain after SLS processes is excellent, sintering temperature
Low, low cost, recycling rate of waterused is high.
Another goal of the invention of the present invention is to provide the preparation method of a kind of PA6/PA66 binary copolymerization material, and it prepares work
Skill is simple, and preparation cost is low, produces stable, and the PA6/PA66 binary copolymerization material obtained is in SLS technique, and part performance is excellent
Different, sintering temperature is low, low cost, and recycling rate of waterused is high.
The purpose of the present invention is achieved through the following technical solutions:
A kind of PA6/PA66 binary copolymerization material, melts copolymerization by caprolactam and adipic acid hexamethylene diamine salt and prepares, acyl in oneself
Amine is 6-9:4-1 with the mass ratio of adipic acid hexamethylene diamine salt.The preferred mass ratio of caprolactam and adipic acid hexamethylene diamine salt is 8:
2。
PA66 has good impact resistance and high intensity, the problem that can effectively make up PA6 notch impact strength difference,
The present invention is polymerized monomer by reasonable coordination PA6's with PA66 so that PA6/PA66 binary copolymerization material melting point is low, and flexibility is more
Greatly, beneficially molecule or the motion of segment and swing, simultaneously because reduce the regularity of strand so that the crystallization of polymer
Degree and crystalline rate reduce.
Wherein, the raw material of this PA6/PA66 binary copolymerization material also includes flow promortor and antioxidant so that PA6/PA66
The particle diameter distribution of binary copolymerization material is more good, and sintering temperature is lower, and is able to ensure that PA6/PA66 binary copolymerization material
Mechanical property.
Wherein, described flow promortor is aerosil, gas phase aluminium sesquioxide, nano titanium oxide and nano silicon carbide
One or more in silicon.
Aerosil has porous, nonpoisonous and tasteless pollution-free, high temperature resistant；It possesses simultaneously chemical inertness and
Special thixotropic property is obviously improved mobility and the tensile strength of PA6/PA66 binary copolymerization material of the present invention, tear resistance and
Wearability, and its mechanical strength can be improved.
Gas phase aluminium sesquioxide be utilize gas-phase process prepare BET surface area be 100 ± 15 particle diameters be 13 nanometers
Aluminium sesquioxide, it joins PA6/PA66 binary copolymerization material of the present invention as flow promortor, it is possible to effectively reduce electrostatic charge
Produce, improve the mobility of powder, improve processability in SLS, it is to avoid moisture absorption, extend storage-stable, increase the end of at
Rheological property on material and edge coverage, compared with meteorological silicon dioxide, gas phase aluminium sesquioxide will not be to the sintering of material
Performance has too much influence.
The color mileage of nano titanium oxide is higher, and heat stability is high, improves the mobility of dusty material, can improve
The sintering strength of PA6/PA66 binary copolymerization material.
Nanometer silicon carbide joins in system of the present invention, improves mobility and the mouldability of dusty material, improves PA6/
The recycling rate of waterused of PA66 binary copolymerization material.
Wherein, described antioxidant is Hinered phenols antioxidant or phosphite ester kind antioxidant, improves PA6/PA66 binary altogether
The sintering character of poly-material, oxidation resistance is strong, improves overall part performance, and can delay or suppress material oxidation mistake
The carrying out of journey, thus stop the aging of product and extend its service life.
Wherein, the mass ratio of described flow promortor and antioxidant and total material is 0.003-0.007:1, flow promortor and
The addition of antioxidant can not be excessive, otherwise can affect the paving powder effect in the integral material SLS course of processing and SLS prints product
Performance, but amount is the most then difficult to reach to improve the mobility of integral material, antioxidant effect and product mouldability, and therefore this mixes
Composition and division in a proportion example can be effectively improved recycling rate of waterused and the sintering character of PA6/PA66 binary copolymerization material.
A kind of preparation method of PA6/PA66 binary copolymerization material, including following preparation process:
(1) caprolactam and adipic acid hexamethylene diamine salt are mixed to join in reactor for 6-9:4-1 in mass ratio；
(2) by the air emptying in reactor, closed reactor, it is warming up to 190-220 DEG C, is incubated 0.5-3 hour, then is warming up to
230-260 DEG C is reacted 1-2 hour, and cooling obtains product；PA6 with PA66 is allowed to react more abundant, the PA6/PA66 obtained
Binary copolymerization material has lower sintering temperature and degree of crystallinity.
(3) product being pulverized, filtering out particle diameter is the dusty material between 20-100 μm；The granular materials of this particle diameter
Can preferably be applicable to SLS processing technique.
(4) dusty material that step 3 obtains is dried.
The preparation method of the present invention makes the PA6/PA66 binary copolymerization material of the present invention obtain lower sintering temperature, and raw
Producing process stabilization, technique is simple, it is easy to manipulation, and the sintering temperature of the PA6/PA66 binary copolymerization material obtained effectively reduces, and
Mechanical property can keep preferable level, is particularly suited for laser sintered material.
Wherein, step (4) dried dusty material adds flow promortor and antioxidant mix homogeneously.
Wherein, the breaking method of described step (3) uses physical pulverization mode, effectively guarantees the chemical of dusty material
Energy.
Wherein, the breaking method of described step (3) uses deep cooling crush, the general burning using deep cooling crush can reduce material
Knot performance, but the present invention preparation-obtained PA6/PA66 binary copolymerization material uses the granule that the mode of deep cooling crush obtains
More uniform, and its sintering character can't be affected.
Wherein, in described step (2), air emptying uses evacuation and is filled with nitrogen 2-6 time.In effectively guaranteeing reactor
The degree of polymerization of material, the PA6/PA66 binary copolymerization material sintering temperature obtained effectively reduces.
The beneficial effects of the present invention is: the present invention uses the method for melt co-polycondensation to prepare PA6/PA66 binary copolymerization material
Material, by regulation caprolactam and the proportioning of adipic acid hexamethylene diamine salt, it is ensured that while excellent mechanical property, reduce molten
Melt temperature (Tm) and crystallization temperature (Tc) so that PA6/PA66 binary copolymerization material has relatively low burning in the SLS course of processing
Junction temperature, lower at least 20 DEG C than the sintering temperature of pure PA6 nylon, alleviate material because being chronically at cause under high temperature serious
Oxidation, improves materials'use rate, is therefore particularly suited for SLS sintering process.
The present invention another advantage is that: the preparation method technique letter of the PA6/PA66 binary copolymerization material of the present invention
Just, easily implement, produce stable, cost-effective, it is highly suitable for the preparation of the raw material of SLS sintering process.
Detailed description of the invention
For the ease of the understanding of those skilled in the art, below in conjunction with embodiment, the present invention is further illustrated, real
The content that the mode of executing is mentioned not limitation of the invention.
Embodiment 1
A kind of preparation method of PA6/PA66 binary copolymerization material, including following preparation process:
(1) caprolactam and adipic acid hexamethylene diamine salt are mixed homogeneously for 9:1 in mass ratio in pulverizer join reactor
In；
(2) vacuum nitrogen filling gas is by the air emptying in reactor, closed reactor, is warming up to 190 DEG C, is incubated 0.5 hour, then
It is warming up to 230 DEG C react 1 hour, reacts complete product being put in water and cool down；
(3) utilizing lapping mode to pulverize product, filtering out particle diameter is the dusty material between 20 μm；
(4) dusty material step 3 obtained adds flow promortor after drying and antioxidant mix homogeneously i.e. obtains PA6/PA66
Binary copolymerization material, described flow promortor and antioxidant are 0.006:1 with the mass ratio of total material.
Embodiment 2
A kind of preparation method of PA6/PA66 binary copolymerization material, including following preparation process:
(1) caprolactam and adipic acid hexamethylene diamine salt are mixed homogeneously for 8:2 in mass ratio in pulverizer join reactor
In；
(2) vacuum nitrogen filling gas is by the air emptying in reactor, closed reactor, is warming up to 220 DEG C, is incubated 3 hours, then rises
Temperature is reacted 2 hours to 260 DEG C, reacts complete product being put in water and cools down；
(3) utilizing lapping mode to pulverize product, filtering out particle diameter is the dusty material between 100 μm；
(4) dusty material step 3 obtained adds flow promortor after drying and antioxidant mix homogeneously i.e. obtains PA6/PA66
Binary copolymerization material, described flow promortor and antioxidant are 0.003:1 with the mass ratio of total material.
Embodiment 3
A kind of preparation method of PA6/PA66 binary copolymerization material, including following preparation process:
(1) caprolactam and adipic acid hexamethylene diamine salt are mixed homogeneously for 6:4 in mass ratio in pulverizer join reactor
In；
(2) vacuum nitrogen filling gas 3 times is by the air emptying in reactor, closed reactor, is warming up to 200 DEG C, is incubated 2 hours,
It is warming up to 250 DEG C again react 1.5 hours, reacts complete product being put in water and cool down；
(3) utilizing lapping mode to pulverize product, filtering out particle diameter is the dusty material between 50 μm；
(4) dusty material step 3 obtained adds flow promortor after drying and antioxidant mix homogeneously i.e. obtains PA6/PA66
Binary copolymerization material, described flow promortor and antioxidant are 0.005:1 with the mass ratio of total material.
Embodiment 4
A kind of preparation method of PA6/PA66 binary copolymerization material, including following preparation process:
(1) caprolactam and adipic acid hexamethylene diamine salt are mixed homogeneously for 7:3 in mass ratio in pulverizer join reactor
In；
(2) vacuum nitrogen filling gas is by the air emptying in reactor, closed reactor, is warming up to 190-220 DEG C, is incubated 0.5-3
Hour, then it is warming up to 230-260 DEG C of reaction 1-2 hour, react complete product being put in water and cool down；
(3) utilizing lapping mode to pulverize product, filtering out particle diameter is the dusty material between 20-100 μm；
(4) dusty material step 3 obtained adds flow promortor after drying and antioxidant mix homogeneously i.e. obtains PA6/PA66
Binary copolymerization material.
Embodiment 5
A kind of preparation method of PA6/PA66 binary copolymerization material, including following preparation process:
(1) caprolactam and adipic acid hexamethylene diamine salt are mixed homogeneously in pulverizer for 6-9:4-1 in mass ratio join anti-
Answer in device；
(2) vacuum nitrogen filling gas is by the air emptying in reactor, closed reactor, is warming up to 190-220 DEG C, is incubated 0.5-3
Hour, then it is warming up to 230-260 DEG C of reaction 1-2 hour, react complete product being put in water and cool down；
(3) utilizing lapping mode to pulverize product, filtering out particle diameter is the dusty material between 20-100 μm；
(4) dusty material step 3 obtained adds flow promortor after drying and antioxidant mix homogeneously i.e. obtains PA6/PA66
Binary copolymerization material, described flow promortor and antioxidant are 0.004:1 with the mass ratio of total material.
By pure PA6 powder as a comparison case, the melt temperature of the PA6/PA66 binary copolymerization material that embodiment 1-5 prepares
Tm and crystallization temperature Tc are as shown in table 1 below:
| Test event | Melt temperature Tm/ DEG C | Crystallization temperature Tc/ DEG C | SLS sintering processing temperature/DEG C |
| PA6 powder | 223.7 | 186.1 | 206 |
| Embodiment 1 | 206.2 | 160.1 | 184 |
| Embodiment 2 | 187.5 | 153.3 | 175 |
| Embodiment 3 | 172.7 | 132.5 | 161 |
| Embodiment 4 | 180.4 | 143.8 | 173 |
| Embodiment 5 | 178.2 | 136.5 | 168 |
By pure PA6 powder as a comparison case, the PA6/PA66 binary copolymerization material that embodiment 1-5 prepares is made after SLS processes
The mechanical property of part is as shown in table 2 below:
| Test event | Tensile strength/MPa | Stretch modulus/MPa | Elongation at break/% |
| PA6 powder | 75.6 | 3950 | 23 |
| Embodiment 1 | 71.3 | 3210 | 34 |
| Embodiment 2 | 66 | 3120 | 20 |
| Embodiment 3 | 64 | 2900 | 7 |
| Embodiment 4 | 63 | 3000 | 10 |
| Embodiment 5 | 64 | 3040 | 12 |
From the data of above-mentioned two table it can be seen that pure PA6 powder is as sintered material, its sintering temperature is up to 206 DEG C, because of
Easy severe oxidation under this long term high temperature sintering temperature；And the sintering temperature of the PA6/PA66 binary copolymerization material entirety of the present invention
Below 200 DEG C, even as low as about 160 DEG C, this greatly reduces the degree of oxidation of sintered material.
On the whole, tensile strength and the modulus of the PA6/PA66 binary copolymerization material of the present invention can decrease than pure PA6,
But the amplitude of reduction is few, sintering character will not be produced impact, therefore, it is possible to before effectively guaranteeing the mechanical property of sintered material
Put and effectively reduce its sintering temperature, the technique being particularly suited for SLS, and the preparation technology of entirety easy, low cost, produce
Stable.
Above-described embodiment is the present invention preferably implementation, and in addition, the present invention can realize with alternate manner,
Without departing from obvious replacement any on the premise of present inventive concept all within protection scope of the present invention.
Claims (10)
1. a PA6/PA66 binary copolymerization material, it is characterised in that: described PA6/PA66 binary copolymerization material is by acyl in oneself
Amine and adipic acid hexamethylene diamine salt melt copolymerization and prepare, and caprolactam is 6-9:4-1 with the mass ratio of adipic acid hexamethylene diamine salt.
A kind of PA6/PA66 binary copolymerization material the most according to claim 1, it is characterised in that: described PA6/PA66 binary
The raw material of copolymeric material also includes flow promortor and/or antioxidant.
A kind of PA6/PA66 binary copolymerization material the most according to claim 2, it is characterised in that: described flow promortor is gas
One or more in aerosil, gas phase aluminium sesquioxide, nano titanium oxide and nanometer silicon carbide.
A kind of PA6/PA66 binary copolymerization material the most according to claim 2, it is characterised in that: described antioxidant is for being obstructed
Phenolic antioxidant or phosphite ester kind antioxidant.
A kind of PA6/PA66 binary copolymerization material the most according to claim 2, it is characterised in that: described flow promortor and/
Or the mass ratio of antioxidant and total raw material is 0.003-0.007:1.
6. the preparation method of a PA6/PA66 binary copolymerization material, it is characterised in that: include following preparation process:
(1) caprolactam and adipic acid hexamethylene diamine salt are mixed to join in reactor for 6-9:4-1 in mass ratio；
(2) by the air emptying in reactor, closed reactor, it is warming up to 190-220 DEG C, is incubated 0.5-3 hour, continue to heat up
React 1-2 hour to 230-260 DEG C, cooling, obtain product；
(3) product being pulverized, filtering out particle diameter is the dusty material between 20-100 μm；
(4) dusty material that step 3 obtains is dried.
The preparation method of a kind of PA6/PA66 binary copolymerization material the most according to claim 6, it is characterised in that: described step
Suddenly in (4), dried dusty material adds flow promortor and antioxidant mix homogeneously.
The preparation method of a kind of PA6/PA66 binary copolymerization material the most according to claim 6, it is characterised in that: described step
Suddenly the breaking method in (3) uses physical pulverization.
The preparation method of a kind of PA6/PA66 binary copolymerization material the most according to claim 6, it is characterised in that: described step
Suddenly the breaking method in (3) uses deep cooling crush.
The preparation method of a kind of PA6/PA66 binary copolymerization material the most according to claim 6, it is characterised in that: described
In step (2), air emptying uses evacuation and is filled with nitrogen 2-6 time.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106977711A (en) * | 2017-04-14 | 2017-07-25 | 湖南华曙高科技有限责任公司 | A kind of selective laser sintering PA66/PA6 copolymeric materials and preparation method |
| US11525035B2 (en) * | 2017-04-27 | 2022-12-13 | Advansix Resins & Chemicals Llc | Method and composition for improved agglomeration resistance of polyamide polymers |
| CN116003782A (en) * | 2022-04-26 | 2023-04-25 | 湖南世博瑞高分子新材料有限公司 | Synthesis method and application of high-flow low-temperature-resistant PA66 resin |
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Application publication date: 20160817 |