CN105949763A - Environment-friendly polyamide composition with good appearance and hot water stability and preparation method of polyamide composition - Google Patents
Environment-friendly polyamide composition with good appearance and hot water stability and preparation method of polyamide composition Download PDFInfo
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- CN105949763A CN105949763A CN201610324094.7A CN201610324094A CN105949763A CN 105949763 A CN105949763 A CN 105949763A CN 201610324094 A CN201610324094 A CN 201610324094A CN 105949763 A CN105949763 A CN 105949763A
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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
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92885—Screw or gear
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to environment-friendly polyamide composition with good appearance and hot water stability and a preparation method of the polyamide composition. The environment-friendly polyamide composition is prepared from components in percentage by weight as follows: 25%-65% of polyamide A, 5%-30% of polyamide B, 25%-50% of glass fibers, 1%-10% of a compatilizer, 0.2%-0.6% of a coupling agent, 0.2%-0.4% of an antioxidant and 0.2%-1% of a lubricant. The invention further provides the preparation method of the composition. The polyamide composition and the preparation method have the advantages as follows: the prepared material has excellent appearance quality and mechanical performance and high hot water resistance retention rate, is environment-friendly and very low in precipitation, meets the requirements of food contact materials and is particularly applicable to the field of high-pressure cleaning and the water contact fields such as daily bathroom equipment accessories and the like.
Description
Technical field
The present invention relates to polymeric material field, specifically, be that a kind of environment-friendly type good outward appearance hot water stably gathers
Amide compositions and preparation method thereof.
Background technology
PA66 is one of yield maximum, the widest kind of purposes in polyamide family, is excellent engineering
Plastics.It has many premium properties such as wear-resisting, self-lubricating, impact resistance, be widely used in automobile, machinery,
The fields such as electronics.But PA66 is big due to water absorption simultaneously, cause size unstable, dry state and hygrometric state
The shortcomings such as energy gap is big.In order to improve this problem, for realizing engineering plastics application, glass fibre is utilized to fill out
Filling enhancing modified is one of means relatively common in industry, but the glass modification of routine not only results in " floating
Fine " and affect final surface quality, the compatibility between the most common glass inorganic matter and macromolecule resin is not
Ideal, conventional modification can not promote anti-hydrolytic performance, limit to a certain extent and particularly contact at water
The application of zone material.High-pressure wash industry development in recent years, water is still modal cleansing medium,
Along with the continuous lifting of resistance to static pressure requirement, need material have higher mechanical strength and water resistance conservation rate with
And the stability of excellence.On the other hand, in life bathroom field, it is limited by copper material and contains lead and cost
Etc. factor, substituting traditional copper material with environment-friendly type engineering plastics is an important trends in industry.
Chinese patent literature CN 102311638B discloses a kind of hydrolysis fiberglass reinforced of resistance to alcoholysis PPA material
Material and preparation method thereof, utilizes the material of its invention preparation to have high resistance to alcoholysis performance, but its performance is not
Can meet the requirement to high detonation pressure intensity, and the cost of raw material is high, production stability is wayward, separates out
Risk is big, is not readily used for life kind water contact zone material.
But about a kind of environment-friendly type good outward appearance hot water stable polyamides compositions and preparation method thereof the most also
Have no report.
Summary of the invention
The invention aims to overcome above-mentioned prior art not enough and provide a kind of environmental protection, cold-resistant hot water steady
Qualitative good, mechanical performance is high, the environment-friendly type of good appearance good outward appearance hot water stable polyamides compositions and system thereof
Preparation Method.
The purpose of the present invention can reach by the following technical programs:
A first aspect of the present invention, it is provided that a kind of environment-friendly type good outward appearance hot water stable polyamides compositions, described
Compositions includes each component of following weight percent content:
Described polyamide A is copolymerization PA66, and hexamethylene diamine adipate forms with caprolactam copolymerization, acyl in oneself
The accounting of amine is 2-15%, can be preferably the PA6685XFS of Shou Nuo company of U.S. production.
Described polyamide B is the one in PA610, PA612, PA1010, PA12, PA1212,
Can be preferably PA610.
Described glass fibre is chopped glass fiber, and fibre length is 3～7mm, its lateral cross section be circular or
Irregular shape changeable structure, can be preferably the HP3660 of PPG company or CSG that day east is spun
3PA-830。
Described compatilizer is PE graft, for PE-g-MAH, in PE-g-GMA, PE-g-AS
Kind, preferably the 5904 of the liter production of Nantong day.
Described coupling agent is amino silicone methane series coupling agent.
Described antioxidant is phosphite ester kind antioxidant and polyhydroxy-alcohol compound system, preferably 168 and double seasons penta
Tetrol compounds by weight 11 and forms.
Described lubricant is the salt containing montanic acid or its copolymer, preferably montanic acid sodium.
A second aspect of the present invention, it is provided that the preparation of above-mentioned environment-friendly type good outward appearance hot water stable polyamides compositions
Method, comprises the following steps:
(1) raw material is dry: by polyamide A, polyamide B in vacuum drying oven, at 100～120 DEG C
At a temperature of be dried 4～8 hours；
(2) after each component in addition to described glass fibre being mixed in feeding machine adds double screw extruder,
Described glass fibre is added by double screw extruder glass entrance, carries out extruding pelletization；
Described processing technique is: the screw speed of double screw extruder controls at 30HZ～45HZ, temperature
Control first paragraph 230～240 DEG C, second segment 250～260 DEG C, the 3rd section 250～260 DEG C, the 4th section 260～
270 DEG C, the 5th section 270～280 DEG C, the 6th section 270～280 DEG C, the 7th section 260～270 DEG C, the 8th section
260～270 DEG C, the 9th section 260～270 DEG C, the tenth section 250～260 DEG C, the 4th section is vacuum with the 9th section
Device, vacuum degree control is less than-0.1MPa.
The invention has the advantages that:
1, the present invention passes through process innovation, arranges vacuum port screw rod the 4th section with the 9th section, at screw rod the
When four sections, resin raw material has plastified completely, and the specific surface area of material is maximum, carries out evacuation in this section, can
Effectively to extract the little molecule volatile matter in resin and auxiliary agent and moisture out, the 5th section to the 8th section is shearing section,
The specific surface area shearing section material diminishes, and mixes completely screw rod the 9th section, is again introduced into material transportation section,
The specific surface area of material becomes big, and now arrange that vacuum can extract out in resin, auxiliary agent and glass further is little
Molecule volatile matter and moisture, obtained material environment friendly safety, little molecule is extracted out, reduces the moisture content of system,
Moisture is similar to little molecule lubricant, disperses section in screw rod shearing, though mobility and the dispersion of glass can be improved
Property, but nylon segment is also more easy to move with shear direction, and therefore nylon segment is difficult to tangle with glass, both
Between interaction force also weakened by hydrone.
2, in glass fiber reinforced materials, resin is equivalent to " armored concrete " with glass combination, the power of material
Learn excellent strength, the chopped glass fiber modified by adding hydrolysis level, improve the reactivity of glass, thus
Improve the binding ability of nylon and glass, further, use PE graft as compatilizer, a side
Face, by graft functional group and the bridge structure that forms " hand in hand " between glass and resin, allows glass
More tight with resin-bonded, improves hydrolysis difficulty；On the other hand, the PE material of the other end is in processing
Under technology controlling and process, form one layer of hydrophobic structure at material surface, protect material internal structure.
3, formula adds copolymerization PA66, owing to the strand regularity of copolymerization PA66 is destroyed, therefore
Its crystal property is poor, and the existence of unformed component can well be coated with glass, can suppress other auxiliary agents simultaneously
Separate out, improve surface property.
4, phosphite ester kind antioxidant and polyhydroxy-alcohol are combined antioxidant system, improve the heat oxygen aging resistance of material
Performance, improves with montanic acid series lubricant agent and processes smooth characteristic and glass dispersion in resin, thus carry
The bulk strength of high material and stability.
5, formula is raw materials used all meets Food Contact level material requirements.
6, the invention provides a kind of stable performance, hydrolysis conservation rate is high, the glass fiber reinforced PA66 of high resistance to static pressure
Composite, this material has presentation quality excellent especially and mechanical performance, and heat-proof water performance conservation rate is high,
Environmental protection, extremely low precipitation, meet Food Contact level material requirements, be particularly well-suited to high-pressure wash field and day
The water contact fields such as normal sanitary bath equipment accessory.
Accompanying drawing explanation
Fig. 1 is the preparation technology flow process signal of the environment-friendly type good outward appearance hot water stable polyamides compositions of the present invention
Figure.
Detailed description of the invention
The detailed description of the invention provided the present invention below in conjunction with embodiment elaborates.
Embodiment 1～6
The present embodiment 1～6 relates to a kind of environment-friendly type good outward appearance hot water stable polyamides compositions, its preparation side
Method comprises the following steps:
(1) getting the raw materials ready according to component and the content of embodiment 1-6 in table 1, wherein polyamide A is common
Poly-nylon, can be preferably the 85XFS of first promise；Polyamide B preferably PA610, glass fibre is
Chopped glass fiber, fibre length is 3～7mm, and its lateral cross section is circular or irregular shape changeable structure, excellent
That select is the HP3660 of PPG；Compatilizer is PE graft, preferably the 5904 of the liter production of Nantong day；
Coupling agent is amino silicone methane series coupling agent, and antioxidant is 168 and Bis(pentaerythritol) compounds by weight 1:1
Form, lubrication dispersing agent is montanic acid sodium.
(2) as it is shown in figure 1, after each raw material components in addition to glass fibre is mixed according to the above ratio through feed
Material machine adds in double screw extruder, and glass fibre is added by double screw extruder glass entrance, extrudes
Pelletize.
Screw speed controls at 30HZ～45HZ, temperature control first paragraph 230～240 DEG C, second segment 250～
260 DEG C, the 3rd section 250～260 DEG C, the 4th section 260～270 DEG C, the 5th section 270～280 DEG C, the 6th section
270～280 DEG C, the 7th section 260～270 DEG C, the 8th section 260～270 DEG C, the 9th section 260～270 DEG C,
Tenth section 250～260 DEG C, the 4th section is vacuum equipment with the 9th section, and vacuum degree control is less than-0.1MPa.
The environment-friendly type good outward appearance hot water stable polyamides compositions that the present embodiment is provided, can contact as water under high pressure
The PP Pipe Compound of zone material.
Table 1
| Raw material/wt% | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Polyamide A | 50.8 | 48.8 | 43.8 | 42.8 | 40.8 | 33.8 |
| Polyamide B | 15 | 15 | 20 | 15 | 10 | 10 |
| Glass fibre | 25 | 30 | 30 | 35 | 40 | 50 |
| Compatilizer | 8 | 5 | 5 | 6 | 8 | 5 |
| Coupling agent | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| Antioxidant | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 |
| Lubricant | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
The material of above-mentioned preparation by iso standard test mechanical performance, and become to clean by corresponding material injection
Press proof product, the isostatic pressing strength after test normality and 24 hours decocting in water, such as table 2 below:
Table 2
As shown in Table 2: the environment-friendly type good outward appearance hot water stable polyamides prepared by embodiment 1-6, surface matter
Measuring, performance is higher, stably meets the test of normality isostatic pressing strength and is more than 50Mpa, and anti-hydrolytic performance is good,
100 DEG C of decocting in water after 24 hours detonation pressure intensity more than 30Mpa, it is adaptable to high-pressure wash field, and life defends
The application requirement in bath water contact field.
The above is only the preferred embodiment of the present invention, it is noted that common for the art
Technical staff, on the premise of without departing from the inventive method, it is also possible to makes some improvement and supplements, these
Improve and supplement and also should be regarded as protection scope of the present invention.
Claims (9)
1. an environment-friendly type good outward appearance hot water stable polyamides compositions, it is characterised in that described compositions is made up of each component of following weight percent content:
Described polyamide A is copolymerization PA66, and fusing point is 240～260 DEG C, and described polyamide B is the one in PA610, PA612, PA1010, PA12, PA1212.
Environment-friendly type the most according to claim 1 good outward appearance hot water stable polyamides compositions, it is characterised in that described copolymerization PA66 is that hexamethylene diamine adipate forms with caprolactam copolymerization, and the accounting of caprolactam is 2～15%.
Environment-friendly type the most according to claim 1 good outward appearance hot water stable polyamides compositions, it is characterised in that described glass fibre is chopped glass fiber, and fibre length is 3～7mm, its lateral cross section is circular or irregular shape changeable structure.
Environment-friendly type the most according to claim 1 good outward appearance hot water stable polyamides compositions, it is characterised in that described compatilizer is PE graft, for PE-g-MAH, at least one in PE-g-GMA, PE-g-AS.
Environment-friendly type the most according to claim 1 good outward appearance hot water stable polyamides compositions, it is characterised in that described coupling agent is amino silicone methane series coupling agent.
Environment-friendly type the most according to claim 1 good outward appearance hot water stable polyamides compositions, it is characterised in that described antioxidant is phosphite ester kind antioxidant and polyhydroxy-alcohol compound system.
Environment-friendly type the most according to claim 1 good outward appearance hot water stable polyamides compositions, it is characterised in that described lubricant is the salt containing montanic acid or its copolymer.
8. the preparation method of environment-friendly type good outward appearance hot water stable polyamides compositions as claimed in claim 1, it is characterised in that comprise the following steps:
(1) raw material is dry: by polyamide A, polyamide B in vacuum drying oven, be dried 4～8 hours at a temperature of 100～120 DEG C；
(2) after each component in addition to described glass fibre being mixed in feeding machine adds double screw extruder, described glass fibre is added by double screw extruder glass entrance, carries out extruding pelletization.
9. the preparation method of environment-friendly type good outward appearance hot water stable polyamides compositions as claimed in claim 8, it is characterized in that, the processing technique of described preparation method is: the screw speed of double screw extruder controls at 30HZ～45HZ, temperature controls first paragraph 230～240 DEG C, second segment 250～260 DEG C, 3rd section 250～260 DEG C, 4th section 260～270 DEG C, 5th section 270～280 DEG C, 6th section 270～280 DEG C, 7th section 260～270 DEG C, 8th section 260～270 DEG C, 9th section 260～270 DEG C, tenth section 250～260 DEG C, 4th section is vacuum equipment with the 9th section, vacuum degree control is less than-0.1MPa.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109943067A (en) * | 2019-03-28 | 2019-06-28 | 江苏晋伦塑料科技有限公司 | A kind of pure hydrolysis daiamid composition and preparation method thereof |
| CN110591344A (en) * | 2019-09-04 | 2019-12-20 | 上海日之升科技有限公司 | Efficient flame-retardant heat-conducting nylon composite material and preparation method thereof |
| WO2021120863A1 (en) * | 2019-12-19 | 2021-06-24 | 金发科技股份有限公司 | Polyamide composition and preparation method therefor |
| CN113544206A (en) * | 2019-01-17 | 2021-10-22 | 弗劳恩霍夫应用研究促进协会 | Use of additive composition for controlled accelerated degradation of polycondensates |
| WO2021212819A1 (en) * | 2020-04-24 | 2021-10-28 | 金发科技股份有限公司 | Polyamide composite material and preparation method therefor |
| CN115181416A (en) * | 2022-07-15 | 2022-10-14 | 华润化学材料科技股份有限公司 | Polyamide engineering plastic and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113544206A (en) * | 2019-01-17 | 2021-10-22 | 弗劳恩霍夫应用研究促进协会 | Use of additive composition for controlled accelerated degradation of polycondensates |
| JP2022518704A (en) * | 2019-01-17 | 2022-03-16 | フラウンホーファー－ゲゼルシャフト ツゥア フェアデルング デア アンゲヴァンドテン フォァシュング エー．ファウ． | Use of additive compositions for controlled degradation promotion of condensed polymers |
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| WO2021120863A1 (en) * | 2019-12-19 | 2021-06-24 | 金发科技股份有限公司 | Polyamide composition and preparation method therefor |
| WO2021212819A1 (en) * | 2020-04-24 | 2021-10-28 | 金发科技股份有限公司 | Polyamide composite material and preparation method therefor |
| CN115181416A (en) * | 2022-07-15 | 2022-10-14 | 华润化学材料科技股份有限公司 | Polyamide engineering plastic and preparation method and application thereof |
| CN115181416B (en) * | 2022-07-15 | 2023-12-22 | 华润化学材料科技股份有限公司 | Polyamide engineering plastic and preparation method and application thereof |
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