CN106366657A - High-heat-resistance high-flow nylon composite material and preparation method thereof - Google Patents
High-heat-resistance high-flow nylon composite material and preparation method thereof Download PDFInfo
- Publication number
- CN106366657A CN106366657A CN201610890231.3A CN201610890231A CN106366657A CN 106366657 A CN106366657 A CN 106366657A CN 201610890231 A CN201610890231 A CN 201610890231A CN 106366657 A CN106366657 A CN 106366657A
- Authority
- CN
- China
- Prior art keywords
- area
- temperature
- nylon
- resin
- heat
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C08L77/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino-carboxylic acids or of polyamines and polycarboxylic acids
-
- 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
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/505—Screws
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- 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)
- Polyamides (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention relates to a high-heat-resistance high-flow nylon composite material and a preparation method thereof. The high-heat-resistance high-flow nylon composite material is prepared from nylon 6T/11 resin, aliphatic polyamide resin, toluene diisocyanate and 2,2'-(1,3-phenylene)-oxazoline, a coupling agent, alkali-free glass fiber, N,N'-ethylidene bis stearamide, N,N'-di(2,2,6,6-tetramethyl-4-piperidyl)-1,3-phthalic diamide, bi(2,6-ditert-butyl-4-methyl phenyl) pentaerythritol diphosphate, a dripping resistance agent and dimethyl silicone oil. The high-heat-resistance high-flow nylon composite material has the advantages of high heat resistance, high liquidity, high tensile strength and low water absorption and can be applied to the fields of electronic appliances, LEDs, automobiles, aerospace, military and the like.
Description
Technical field
The present invention relates to Material Field, more particularly to a kind of high heat-resisting high flowing nylon composite materials and its preparation side
Method.
Background technology
High temperature resistant nylon is typically by aliphatic diamidogen and aromatic diacid, or aromatic diamidogen and aliphatic
Diacid be prepared through polycondensation.Due to introducing phenyl ring on molecular backbone, high temperature resistant nylon not only maintains aliphatic Buddhist nun
The mechanical property that dragon has is good, acid and alkali-resistance and the advantages of self lubricity, also overcomes that its water absorption rate is high, not good the lacking of dimensional stability
Point, so as to be particularly well-suited in auto industry, in order to replace the part metals structural member in automobile, to realize lightweight, also may be used
With the insulating body for manufacturing electronic device, or it is used for surface mounting technique.
Industrialized high temperature resistant nylon mainly has nylon 6t (copolymer), nylon 9 t, nylon 10t etc..Nylon 6t resin
Fusing point is 370 DEG C about, and it alreadys exceed decomposition temperature, actually can not carry out melt-processed it is necessary to add the 3rd group
The monomer dividing makes the melt temperature of polymer be down to less than 320 DEG C.But, add the Third monomer of low content to be not enough to improve it
Processing characteristics, and the range of work is too narrow, and add the Third monomer of high-load that the fusing point of copolymer resin can be made too low, reach not
To resistant to elevated temperatures requirement.
For above-mentioned problem, in currently available technology, the modification of nylon is done with some researchs, such as Chinese patent cn
103333335a discloses a kind of high fluidity pa10t Amilan polyamide resin composition, and it is obtained by solid phase by two kinds
The pa10t polyamide composition of different viscositys；It is fire-retardant poly- that Chinese patent cn102604380a discloses a kind of high heat-resisting high cti
Amide composite, wherein this polyamide are polyhexamethylene adipamide/poly-paraphenylene terephthalamide's nonamethylene diamine copolymer or poly- right
Phenyl-diformyl nonamethylene diamine；Chinese patent cn 103030972a disclose a kind of high heat-resisting low-warpage nylon dragon 66 composites and its
Preparation method；Chinese patent cn 103012955a discloses a kind of high flowing fiberglass reinforced pp/pa composite and its preparation side
Method；Chinese patent cn 103724979a discloses a kind of high flowing heatproof led ppo/pa compositionss and preparation method thereof.
Content of the invention
The present invention be directed to the deficiencies in the prior art are it is therefore an objective to provide one kind to have high heat-resisting, high fluidity, high stretching strong
Degree and the nylon composite materials of low water absorption, can serve as electrical/electronic components, automobile component, are particularly useful as electronics
The molding substrate material of part.
For reaching above-mentioned purpose, the present invention adopts below scheme:
A kind of high heat-resisting high flowing nylon composite materials, this composite is prepared from by the raw material of following weight portion:
The intrinsic viscosity of described nylon 6t/11 resin is 0.7～1.0dl/g.
Described amorphous nylon resins are nylon 46 resin (pa46), polyhexamethylene adipamide resin (pa66)
In at least one.
Described coupling agent be gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, n- (β-aminoethyl)-
Gamma-aminopropyl-triethoxy-silane, n- β-(aminoethyl)-γ-aminopropyltrimethoxysilane, n- β-(aminoethyl)-γ-ammonia third
Ylmethyl dimethoxysilane, γ-aminopropyltriethoxy dimethoxysilane, γ-aminopropyltriethoxy diethoxy silane, aniline first
At least one in ethyl triethoxy silicane alkane.
The length of described alkali-free glass fibre is 2～4mm, a diameter of 9～11 μm.
Described anti-dripping agent is fluoropolymer.
Wherein in some embodiments, high heat-resisting high flowing nylon composite materials, by the raw material preparation of following weight portion
Become:
Wherein in some embodiments, high heat-resisting high flowing nylon composite materials, further preferably by following weight portion
Raw material is prepared from:
Wherein in some embodiments, the intrinsic viscosity of described nylon 6t/11 resin is 0.75～0.95dl/g；Described fat
Fat race nylon resin is polyhexamethylene adipamide resin (pa66), and its intrinsic viscosity is 1.22～1.84dl/g.
Wherein in some embodiments, described coupling agent is gamma-aminopropyl-triethoxy-silane, γ-aminopropyl trimethoxy
At least one in base silane；Described anti-dripping agent is politef.
Wherein in some embodiments, described nylon 6t/11 resin is formed by monomer 1 and polyesteramide copolymerization, described list
Body 1 is the hexamethylene diamine of 1:1:0.45～0.55, p-phthalic acid, 11- aminoundecanoic acid for mol ratio, and described polyesteramide adds
Measure 1～8% for described monomer 1 gross weight.
Wherein in some embodiments, described nylon 6t/11 resin is obtained by following synthetic method:
(1) the described monomer 1 after vacuum drying is added in stirring-type polymer reactor, is simultaneously introduced described polyester acyl
Amine, and molecular weight regulator, antioxidant, water；Then evacuation 4～6min, logical nitrogen 4～6min, so circulate 5～7 times,
So that reactant is present in the lower environment of nitrogen protection, control in described stirring-type polymer reactor system pressure for 0.2～
0.3mpa；
(2) in 2～4 hours by airtight for described stirring-type polymer reactor constant-speed heating to 272～280 DEG C, adjust institute
The mixing speed stating stirring-type polymer reactor is 30～50r/min, wherein, when described stirring-type polymer reactor temperature reaches
When 215 DEG C, it is deflated to 2.0mpa, and maintains pressure in 2.0mpa, after reacting 1～2 hour, be deflated to normal pressure, be warming up to simultaneously
After continuing reaction at 310～320 DEG C 1～2 hour, constant temperature continued evacuation after 0.3～1 hour, obtained described nylon 6t/11 tree
Fat；
Described molecular weight regulator is addition is described monomer 1 gross weight 0.1～3% benzoic acid；Described antioxygen
Agent is addition is described monomer 1 gross weight 0.1～0.3% n, n'- bis- (2,2,6,6- tetramethyl -4- piperidyl) -1,
3- benzene diamides；Appropriate amount of water.
It is a further object of the present invention to provide the preparation method of high heat-resisting high flowing nylon composite materials.
The preparation method of the heat-resisting high flowing nylon composite materials of above-mentioned height, specific technical scheme, comprise the following steps:
(1) described nylon 6t/11 resin (pa6t/11) and amorphous nylon resins are placed in 80～100 DEG C, dry 4～
After 12 hours, cooling, by the nylon 6t/11 resin after cooling, amorphous nylon resins, and described toluene di-isocyanate(TDI)
(tdi) double (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzene of, 2,2'- (1,3- phenylene)-bisoxazoline (pbo), n, n'-
Diformamide, double (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-dripping agent and dimethicone add
Mixed in homogenizer；
(2) by described coupling agent, alkali-free glass fibre and n, n'- ethylenebisstearamide is added to another high-speed stirring
Mix in machine and mixed；
(3) compound that step (1) mixes is added in parallel double-screw extruder through feeder, and in parallel pair of spiral shell
Lateral (the such as the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) mixes to be melt extruded, pelletize,
Technological parameter is as follows: area's temperature is 260～290 DEG C, and two area's temperature are 290～305 DEG C, and three area's temperature are 295～310 DEG C,
Four area's temperature are 300～310 DEG C, and five area's temperature are 300～310 DEG C, and six area's temperature are 300～310 DEG C, and seven area's temperature are 300
～310 DEG C, eight area's temperature are 300～310 DEG C, and die head temperature is 295～305 DEG C, and screw speed is 200～600rpm.
Wherein in some embodiments, in described step (1), described nylon 6t/11 resin and amorphous nylon resins are put
In 90 DEG C, it is dried 4～6 hours；Technological parameter in described step (3) is: area's temperature is 260～285 DEG C, and two area's temperature are
290～300 DEG C, three area's temperature are 295～305 DEG C, and four area's temperature are 300～305 DEG C, and five area's temperature are 300～305 DEG C, six
Area's temperature be 300～305 DEG C, seven area's temperature be 300～305 DEG C, eight area's temperature be 300～305 DEG C, die head temperature be 295～
300 DEG C, screw speed is 200～400rpm.
Wherein in some embodiments, the screw configuration of described parallel double-screw extruder is single thread；Spiro rod length l
Ratio l/d with diameter d is 35～50；Described screw rod is provided with the gear block area of more than 1 (containing 1) and more than 1 (containing 1)
Left-hand thread area.
Wherein in some embodiments, the ratio l/d of described spiro rod length l and diameter d is 35～45；Described screw rod is provided with
2 gear block areas and 1 left-hand thread area.
Wherein in some embodiments, described nylon 6t/11 resin is formed by monomer 1 and polyesteramide copolymerization, described list
Body 1 is the hexamethylene diamine of 1:1:0.45～0.55, p-phthalic acid, 11- aminoundecanoic acid for mol ratio, and described polyesteramide adds
Measure 1～8% for described monomer 1 gross weight.
Wherein in some embodiments, described nylon 6t/11 resin is obtained by following synthetic method:
(1) the described monomer 1 after vacuum drying is added in stirring-type polymer reactor, is simultaneously introduced described polyester acyl
Amine, and molecular weight regulator, antioxidant, water；Then evacuation 4～6min, logical nitrogen 4～6min, so circulate 5～7 times,
So that reactant is present in the lower environment of nitrogen protection, control in described stirring-type polymer reactor system pressure for 0.2～
0.3mpa；
(2) in 2～4 hours by airtight for described stirring-type polymer reactor constant-speed heating to 272～280 DEG C, adjust institute
The mixing speed stating stirring-type polymer reactor is 30～50r/min, wherein, when described stirring-type polymer reactor temperature reaches
When 215 DEG C, it is deflated to 2.0mpa, and maintains pressure in 2.0mpa, after reacting 1～2 hour, be deflated to normal pressure, be warming up to simultaneously
After continuing reaction at 310～320 DEG C 1～2 hour, constant temperature continued evacuation after 0.3～1 hour, obtained described nylon 6t/11 tree
Fat；
Described molecular weight regulator is addition is described monomer 1 gross weight 0.1～3% benzoic acid；Described antioxygen
Agent is addition is described monomer 1 gross weight 0.1～0.3% n, n'- bis- (2,2,6,6- tetramethyl -4- piperidyl) -1,
3- benzene diamides；Appropriate amount of water.
The principle of the present invention is as follows:
In order to solve the processing temperature narrow limits of nylon 6t/11 resin and the defect that processing characteristics is not good, the present invention adopts
Improve the processing characteristics of nylon 6t/11 resin with amorphous nylon resins, this is because amorphous nylon resins possess preferably
Mobile performance, and nylon 6t/11 resin possesses preferably mechanical property.Meanwhile, amorphous nylon resins and nylon 6t/11
The end group of resin can respectively with the isocyanate groups of toluene di-isocyanate(TDI), 2,2'- (1,3- phenylene)-bisoxazoline
Oxazoline group reacts, and improves the compatibility of both nylon resins.Meanwhile, the NCO of toluene di-isocyanate(TDI)
Group, the oxazoline group of 2,2'- (1,3- phenylene)-bisoxazoline can also be carried out instead with the coupling agent on alkali-free glass fibre
Should, improve interface binding power and the compatibility of alkali-free glass fibre and above two nylon resin, reduce the floating fine probability occurring.
The coupling agent that the present invention adopts, preferably gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane,
All contain amino, and anti-glass emergence on the surface agent n, n'- ethylenebisstearamide contains amide group, above-mentioned auxiliary agent all can be with
The end group of above two nylon resin reacts, thus improving alkali-free glass fibre and above two nylon resin further
Interface binding power and the compatibility, reduce the floating fine probability occurring.
The length of alkali-free glass fibre and diameter are larger to the mechanical property of nylon resin composite and appearance effects.
The length of alkali-free glass fibre is bigger, and the tensile property of its resin composite materials is higher, simultaneously the probability of glass emergence on the surface also with
Increase；The diameter of alkali-free glass fibre is less, and tensile strength is higher, but the cost of its preparation is higher, unit area simultaneously
Required coupling agent is also more.Therefore, select the length of suitable alkali-free glass fibre and diameter is excellent to processability and property
Valency is just particularly important than high nylon resin composite.
The fusing point of double (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamide of n, n'- is 272 DEG C, boiling point is more than
360 DEG C, the better heat stability in nylon resin composite Blending Processes, its amide group can be with above two nylon
The end group of resin reacts and to improve the compatibility, the dyeability that hindered piperidine base can provide antioxidation and improve copolymer.
The fusing point of double (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate is 239 DEG C, heat decomposition temperature surpasses
Cross 350 DEG C, there is good thermostability and hydrolytic resistance, can be superior for providing in nylon resin composite Blending Processes
Colour stability and melt stability, can prevent thermal degradation in pyroprocess for the above two nylon resin simultaneously, and suppress
Due to long-time and hot oxygen variable color that cause, it also offers in nitrogen oxides (nox) colour stable in the environment of gas
Property, prevent gas from smoking variable color.
Compared with prior art, the method have the advantages that
The present invention is directed to the processing temperature narrow limits of existing nylon 6t/11 resin and the defect that processing characteristics is not good, leads to
Cross the processing characteristics to improve nylon 6t/11 resin using amorphous nylon resins, adopt toluene di-isocyanate(TDI) and 2 simultaneously,
2'- (1,3- phenylene)-bisoxazoline is used as the compatilizer between both nylon resins, and above two nylon resin
Compatilizer and alkali-free glass fibre between, and add coupling agent and n, n'- ethylenebisstearamide is solving floating fibre
Problem, compounding use n, double (2,2,6,6- tetramethyl -4- piperidyl) -1, the 3- benzenedicarboxamide of n'- and double (2,6- bis- tertiary fourths
Base -4- aminomethyl phenyl) pentaerythritol diphosphate to be processing the xanthochromia problem in Blending Processes, preparation-obtained high heat-resisting height
Flowing nylon composite materials have the characteristics that high heat-resisting, high fluidity, high tensile and low water absorption, can be applicable to electronics electricity
Device field, led field, automotive field, Aero-Space and military industry field etc..
Brief description
Fig. 1 show the preparation technology flow chart of the high heat-resisting high flowing nylon composite materials of the present invention.
Specific embodiment
By feature, technological means and the specific purposes being reached, the function of the present invention can be further appreciated that, parse this
Bright advantage and spirit, by following examples, the present invention is further elaborated.
The reaction mechanism of the high heat-resisting high flowing nylon composite materials of the present invention is following (preparation technology flow chart asks for an interview Fig. 1):
Reaction mechanism
From above-mentioned reaction equation, the Amino End Group of amorphous nylon resins and nylon 6t/11 resin can be different with toluene two
The isocyanate groups of cyanate react, and the Amino End Group of amorphous nylon resins and nylon 6t/11 resin, end carboxyl are permissible
React with the oxazoline group of 2,2'- (1,3- phenylene)-bisoxazoline, such that it is able to increase both nylon resins it
Between the compatibility.
The raw material that the embodiment of the present invention is used is as follows:
Nylon 6t/11 resin (pa6t/11), self-control, the hexamethylene diamine in raw material is selected from Wuxi Yinda Nylon Co., Ltd., right
Phthalic acid is selected from Beijing Yanshan Petrochemical Co., and 11- aminoundecanoic acid is selected from Taiyuan Zhong Lianze agrochemicals company limited, its
Remaining auxiliary agent is selected from Chemical Reagent Co., Ltd., Sinopharm Group；
Polyhexamethylene adipamide resin (pa66), selected from China Shenma Group Co., Ltd., its intrinsic viscosity is respectively
1.22dl/g、1.66dl/g、1.84dl/g；
Toluene di-isocyanate(TDI), selected from Chemical Reagent Co., Ltd., Sinopharm Group；
2,2'- (1,3- phenylene)-bisoxazoline, selected from Chemical Reagent Co., Ltd., Sinopharm Group；
Coupling agent (gamma-aminopropyl-triethoxy-silane), selected from Organic Silicon New Material Co. Ltd., Wuhan Univ., Hubei；
Coupling agent (γ-aminopropyltrimethoxysilane), selected from Zhejiang boiling point Chemical Co., Ltd.；
Alkali-free glass fibre, selected from Chinese megalith limited company, length is 3mm, a diameter of 10 μm；
N, n'- ethylenebisstearamide, selected from Guangzhou Bo Han Chemical Co., Ltd.；
Double (2,2,6,6- tetramethyl -4- piperidyl) -1, the 3- benzenedicarboxamide of n, n'-, has selected from such as Dong Jinkangtai chemistry
Limit company；
Double (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, limited selected from Shanghai point credit fine chemistry industry
Company；
Anti-dripping agent (politef), selected from Minnesota ,USA mines and manufacturing industry company；
Dimethicone, selected from Dow corning company.
To describe the present invention below in conjunction with specific embodiment in detail.
Nylon 6t/11 resin in following examples is formed by monomer 1 and polyesteramide copolymerization, described monomer 1 be mole
For the hexamethylene diamine of 1:1:0.45～0.55, p-phthalic acid, 11- aminoundecanoic acid, described polyesteramide addition is described to ratio
The 1～8% of monomer 1 gross weight, above-mentioned nylon 6t/11 resin has as following formula i structure:
In formula i, a=10～200, b=10～200, c=10～100, r is polyesteramide, and it has as following formula ii knot
Structure:
In formula ii, x=10～200, y=10～200, z=10～100.
The synthetic method of nylon 6t/11 resin is as follows:
(1) the described monomer 1 after vacuum drying is added in stirring-type polymer reactor, is simultaneously introduced described polyester acyl
Amine, and molecular weight regulator, antioxidant, water；Then evacuation 4～6min, logical nitrogen 4～6min, so circulate 5～7 times,
So that reactant is present in the lower environment of nitrogen protection, control in described stirring-type polymer reactor system pressure for 0.2～
0.3mpa；
(2) in 2～4 hours by airtight for described stirring-type polymer reactor constant-speed heating to 272～280 DEG C, adjust institute
The mixing speed stating stirring-type polymer reactor is 30～50r/min, wherein, when described stirring-type polymer reactor temperature reaches
When 215 DEG C, it is deflated to 2.0mpa, and maintains pressure in 2.0mpa, after reacting 1～2 hour, be deflated to normal pressure, be warming up to simultaneously
After continuing reaction at 310～320 DEG C 1～2 hour, constant temperature continued evacuation after 0.3～1 hour, obtained described nylon 6t/11 tree
Fat；
Described molecular weight regulator is addition is described monomer 1 gross weight 0.1～3% benzoic acid；Described antioxygen
Agent is addition is described monomer 1 gross weight 0.1～0.3% n, n'- bis- (2,2,6,6- tetramethyl -4- piperidyl) -1,
3- benzene diamides；Appropriate amount of water.
Embodiment 1
The raw material of the nylon 6t/11 resin used in the present embodiment is constituted and synthesis step is as follows:
(1) by the monomer 1:1mol hexamethylene diamine after vacuum drying, 1mol p-phthalic acid, 0.5mol 11- aminoundecanoic acid
Be added in stirring-type polymer reactor, be simultaneously introduced 4% polyesteramide of monomer 1 gross weight, 1.5% benzoic acid,
0.2% n, n'- bis- (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzene diamides, addition 100ml water are as mass-and heat-transfer
Medium；Then evacuation 5min, logical nitrogen 5min, so circulation 6 times, make the environment that reactant is present under nitrogen protection
In, control system pressure in stirring-type polymer reactor to be 0.3mpa；
(2) in 3 hours by airtight for stirring-type polymer reactor constant-speed heating to 275 DEG C, adjust stirring-type polyreaction
The mixing speed of device is 40r/min, wherein, when stirring-type polymer reactor temperature reaches 215 DEG C, is deflated to 2.0mpa, and
Maintain pressure in 2.0mpa, after reacting 1.5 hours, be deflated to normal pressure, be warming up at 315 DEG C after continuing reaction 1.5 hours simultaneously,
Constant temperature continued evacuation after 0.5 hour, obtained described nylon 6t/11 resin；
The intrinsic viscosity of the above-mentioned nylon 6t/11 resin preparing is 0.86dl/g, melt temperature is 299 DEG C.
A kind of high heat-resisting high flowing nylon composite materials of the present embodiment, are prepared from by the following raw material:
The preparation method of the heat-resisting high flowing nylon composite materials of above-mentioned height, comprises the following steps:
(1) described nylon 6t/11 resin and polyhexamethylene adipamide resin are placed in 90 DEG C, after being dried 5 hours, cooling,
By the nylon 6t/11 resin after cooling, polyhexamethylene adipamide resin, and toluene di-isocyanate(TDI) (tdi), 2,2'- (1,3-
Phenylene)-bisoxazoline (pbo), n, n'- double (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzenedicarboxamide, double (2,6-
Di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-dripping agent (politef) and dimethicone be added to height
Mixed in fast blender；
(2) by coupling agent (γ-aminopropyltrimethoxysilane), alkali-free glass fibre and n, n'- ethylenebis stearoyl
Amine is added in another homogenizer and is mixed；
(3) compound that step (1) mixes is added in parallel double-screw extruder through feeder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) mixes to be melt extruded, pelletize, technique
Parameter is as follows: area's temperature is 290 DEG C, and two area's temperature are 305 DEG C, and three area's temperature are 310 DEG C, and four area's temperature are 310 DEG C, 5th area
Temperature is 310 DEG C, and six area's temperature are 310 DEG C, and seven area's temperature are 310 DEG C, and eight area's temperature are 310 DEG C, and die head temperature is 305 DEG C,
Screw speed is 600rpm.
The screw configuration of described parallel double-screw extruder is single thread, and the ratio l/d of spiro rod length l and diameter d is 35,
Described screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Embodiment 2
The raw material of the nylon 6t/11 resin used in the present embodiment is constituted and synthesis step is with embodiment 1.
A kind of high heat-resisting high flowing nylon composite materials of the present embodiment, are prepared from by the following raw material:
The preparation method of the heat-resisting high flowing nylon composite materials of above-mentioned height, comprises the following steps:
(1) described nylon 6t/11 resin and polyhexamethylene adipamide resin are placed in 90 DEG C, after being dried 5 hours, cooling,
By the nylon 6t/11 resin after cooling, polyhexamethylene adipamide resin, and toluene di-isocyanate(TDI) (tdi), 2,2'- (1,3-
Phenylene)-bisoxazoline (pbo), n, n'- double (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzenedicarboxamide, double (2,6-
Di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-dripping agent (politef) and dimethicone be added to height
Mixed in fast blender；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and n, n'- ethylenebis stearoyl
Amine is added in another homogenizer and is mixed；
(3) compound that step (1) mixes is added in parallel double-screw extruder through feeder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) mixes to be melt extruded, pelletize, technique
Parameter is as follows: area's temperature is 260 DEG C, and two area's temperature are 290 DEG C, and three area's temperature are 295 DEG C, and four area's temperature are 300 DEG C, 5th area
Temperature is 300 DEG C, and six area's temperature are 300 DEG C, and seven area's temperature are 300 DEG C, and eight area's temperature are 300 DEG C, and die head temperature is 295 DEG C,
Screw speed is 200rpm.
The screw configuration of described parallel double-screw extruder is single thread, and the ratio l/d of spiro rod length l and diameter d is 50,
Described screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Embodiment 3
The raw material of the nylon 6t/11 resin used in the present embodiment is constituted and synthesis step is with embodiment 1.
A kind of high heat-resisting high flowing nylon composite materials of the present embodiment, are prepared from by the following raw material:
The preparation method of the heat-resisting high flowing nylon composite materials of above-mentioned height, comprises the following steps:
(1) described nylon 6t/11 resin and polyhexamethylene adipamide resin are placed in 90 DEG C, after being dried 5 hours, cooling,
By the nylon 6t/11 resin after cooling, polyhexamethylene adipamide resin, and toluene di-isocyanate(TDI) (tdi), 2,2'- (1,3-
Phenylene)-bisoxazoline (pbo), n, n'- double (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzenedicarboxamide, double (2,6-
Di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-dripping agent (politef) and dimethicone be added to height
Mixed in fast blender；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and n, n'- ethylenebis stearoyl
Amine is added in another homogenizer and is mixed；
(3) compound that step (1) mixes is added in parallel double-screw extruder through feeder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) mixes to be melt extruded, pelletize, technique
Parameter is as follows: area's temperature is 285 DEG C, and two area's temperature are 300 DEG C, and three area's temperature are 305 DEG C, and four area's temperature are 305 DEG C, 5th area
Temperature is 305 DEG C, and six area's temperature are 305 DEG C, and seven area's temperature are 305 DEG C, and eight area's temperature are 305 DEG C, and die head temperature is 300 DEG C,
Screw speed is 400rpm.
The screw configuration of described parallel double-screw extruder is single thread, and the ratio l/d of spiro rod length l and diameter d is 45,
Described screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Embodiment 4
The raw material of the nylon 6t/11 resin used in the present embodiment is constituted and synthesis step is with embodiment 1.
A kind of high heat-resisting high flowing nylon composite materials of the present embodiment, are prepared from by the following raw material:
The preparation method of the heat-resisting high flowing nylon composite materials of above-mentioned height, comprises the following steps:
(1) described nylon 6t/11 resin and polyhexamethylene adipamide resin are placed in 90 DEG C, after being dried 5 hours, cooling,
By the nylon 6t/11 resin after cooling, polyhexamethylene adipamide resin, and toluene di-isocyanate(TDI) (tdi), 2,2'- (1,3-
Phenylene)-bisoxazoline (pbo), n, n'- double (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzenedicarboxamide, double (2,6-
Di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-dripping agent (politef) and dimethicone be added to height
Mixed in fast blender；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and n, n'- ethylenebis stearoyl
Amine is added in another homogenizer and is mixed；
(3) compound that step (1) mixes is added in parallel double-screw extruder through feeder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) mixes to be melt extruded, pelletize, technique
Parameter is as follows: area's temperature is 280 DEG C, and two area's temperature are 295 DEG C, and three area's temperature are 300 DEG C, and four area's temperature are 305 DEG C, 5th area
Temperature is 305 DEG C, and six area's temperature are 305 DEG C, and seven area's temperature are 300 DEG C, and eight area's temperature are 300 DEG C, and die head temperature is 300 DEG C,
Screw speed is 300rpm.
The screw configuration of described parallel double-screw extruder is single thread, and the ratio l/d of spiro rod length l and diameter d is 40,
Described screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Embodiment 5
The raw material of the nylon 6t/11 resin used in the present embodiment is constituted and synthesis step is with embodiment 1.
A kind of high heat-resisting high flowing nylon composite materials of the present embodiment, are prepared from by the following raw material:
The preparation method of the heat-resisting high flowing nylon composite materials of above-mentioned height, comprises the following steps:
(1) described nylon 6t/11 resin and polyhexamethylene adipamide resin are placed in 90 DEG C, after being dried 5 hours, cooling,
By the nylon 6t/11 resin after cooling, polyhexamethylene adipamide resin, and toluene di-isocyanate(TDI) (tdi), 2,2'- (1,3-
Phenylene)-bisoxazoline (pbo), n, n'- double (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzenedicarboxamide, double (2,6-
Di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-dripping agent (politef) and dimethicone be added to height
Mixed in fast blender；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and n, n'- ethylenebis stearoyl
Amine is added in another homogenizer and is mixed；
(3) compound that step (1) mixes is added in parallel double-screw extruder through feeder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) mixes to be melt extruded, pelletize, technique
Parameter is as follows: area's temperature is 280 DEG C, and two area's temperature are 295 DEG C, and three area's temperature are 300 DEG C, and four area's temperature are 305 DEG C, 5th area
Temperature is 305 DEG C, and six area's temperature are 305 DEG C, and seven area's temperature are 300 DEG C, and eight area's temperature are 300 DEG C, and die head temperature is 300 DEG C,
Screw speed is 300rpm.
The screw configuration of described parallel double-screw extruder is single thread, and the ratio l/d of spiro rod length l and diameter d is 40,
Described screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Embodiment 6
The raw material of the nylon 6t/11 resin used in the present embodiment is constituted and synthesis step is with embodiment 1.
A kind of high heat-resisting high flowing nylon composite materials of the present embodiment, are prepared from by the following raw material:
The preparation method of the heat-resisting high flowing nylon composite materials of above-mentioned height, comprises the following steps:
(1) described nylon 6t/11 resin and polyhexamethylene adipamide resin are placed in 90 DEG C, after being dried 5 hours, cooling,
By the nylon 6t/11 resin after cooling, polyhexamethylene adipamide resin, and toluene di-isocyanate(TDI) (tdi), 2,2'- (1,3-
Phenylene)-bisoxazoline (pbo), n, n'- double (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzenedicarboxamide, double (2,6-
Di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-dripping agent (politef) and dimethicone be added to height
Mixed in fast blender；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and n, n'- ethylenebis stearoyl
Amine is added in another homogenizer and is mixed；
(3) compound that step (1) mixes is added in parallel double-screw extruder through feeder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) mixes to be melt extruded, pelletize, technique
Parameter is as follows: area's temperature is 280 DEG C, and two area's temperature are 295 DEG C, and three area's temperature are 300 DEG C, and four area's temperature are 305 DEG C, 5th area
Temperature is 305 DEG C, and six area's temperature are 305 DEG C, and seven area's temperature are 300 DEG C, and eight area's temperature are 300 DEG C, and die head temperature is 300 DEG C,
Screw speed is 300rpm.
The screw configuration of described parallel double-screw extruder is single thread, and the ratio l/d of spiro rod length l and diameter d is 40,
Described screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Comparative example 1
The raw material of the nylon 6t/11 resin used in this comparative example is constituted and synthesis step is with embodiment 1.
A kind of high heat-resisting high flowing nylon composite materials of this comparative example, are prepared from by the following raw material:
The preparation method of the heat-resisting high flowing nylon composite materials of above-mentioned height, comprises the following steps:
(1) described nylon 6t/11 resin is placed in 90 DEG C, after being dried 5 hours, cooling, by the nylon 6t/11 tree after cooling
Fat, and n, n'- double (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzenedicarboxamide, double (2,6- di-t-butyl -4- methyl
Phenyl) pentaerythritol diphosphate, anti-dripping agent (politef) and dimethicone be added in homogenizer and carry out
Mixing；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and n, n'- ethylenebis stearoyl
Amine is added in another homogenizer and is mixed；
(3) compound that step (1) mixes is added in parallel double-screw extruder through feeder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) mixes to be melt extruded, pelletize, technique
Parameter is as follows: area's temperature is 280 DEG C, and two area's temperature are 295 DEG C, and three area's temperature are 300 DEG C, and four area's temperature are 305 DEG C, 5th area
Temperature is 305 DEG C, and six area's temperature are 305 DEG C, and seven area's temperature are 300 DEG C, and eight area's temperature are 300 DEG C, and die head temperature is 300 DEG C,
Screw speed is 300rpm.
The screw configuration of described parallel double-screw extruder is single thread, and the ratio l/d of spiro rod length l and diameter d is 40,
Described screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Comparative example 2
The raw material of the nylon 6t/11 resin used in this comparative example is constituted and synthesis step is with embodiment 1.
A kind of high heat-resisting high flowing nylon composite materials of this comparative example, are prepared from by the following raw material:
The preparation method of the heat-resisting high flowing nylon composite materials of above-mentioned height, comprises the following steps:
(1) described nylon 6t/11 resin and polyhexamethylene adipamide resin are placed in 90 DEG C, after being dried 5 hours, cooling,
By the nylon 6t/11 resin after cooling, polyhexamethylene adipamide resin, and n, double (2,2,6, the 6- tetramethyl -4- piperidines of n'-
Base) -1,3- benzenedicarboxamide, double (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-dripping agent (poly- four
Fluorothene) and dimethicone be added in homogenizer and mixed；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and n, n'- ethylenebis stearoyl
Amine is added in another homogenizer and is mixed；
(3) compound that step (1) mixes is added in parallel double-screw extruder through feeder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) mixes to be melt extruded, pelletize, technique
Parameter is as follows: area's temperature is 280 DEG C, and two area's temperature are 295 DEG C, and three area's temperature are 300 DEG C, and four area's temperature are 305 DEG C, 5th area
Temperature is 305 DEG C, and six area's temperature are 305 DEG C, and seven area's temperature are 300 DEG C, and eight area's temperature are 300 DEG C, and die head temperature is 300 DEG C,
Screw speed is 300rpm.
The screw configuration of described parallel double-screw extruder is single thread, and the ratio l/d of spiro rod length l and diameter d is 40,
Described screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Comparative example 3
The raw material of the nylon 6t/11 resin used in this comparative example is constituted and synthesis step is with embodiment 1.
A kind of high heat-resisting high flowing nylon composite materials of this comparative example, are prepared from by the following raw material:
The preparation method of the heat-resisting high flowing nylon composite materials of above-mentioned height, comprises the following steps:
(1) described nylon 6t/11 resin and polyhexamethylene adipamide resin are placed in 90 DEG C, after being dried 5 hours, cooling,
By the nylon 6t/11 resin after cooling, polyhexamethylene adipamide resin, and toluene di-isocyanate(TDI) (tdi), 2,2'- (1,3-
Phenylene)-bisoxazoline (pbo), n, n'- double (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzenedicarboxamide, double (2,6-
Di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-dripping agent (politef) and dimethicone be added to height
Mixed in fast blender；
(2) compound that step (1) mixes is added in parallel double-screw extruder through feeder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds alkali-free glass fibre to be melt extruded, pelletize, and technological parameter is as follows:
One area's temperature is 280 DEG C, and two area's temperature are 295 DEG C, and three area's temperature are 300 DEG C, and four area's temperature are 305 DEG C, and five area's temperature are 305
DEG C, six area's temperature are 305 DEG C, and seven area's temperature are 300 DEG C, and eight area's temperature are 300 DEG C, and die head temperature is 300 DEG C, and screw speed is
300rpm.
The screw configuration of described parallel double-screw extruder is single thread, and the ratio l/d of spiro rod length l and diameter d is 40,
Described screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Comparative example 4
The raw material of the nylon 6t/11 resin used in this comparative example is constituted and synthesis step is with embodiment 1.
A kind of high heat-resisting high flowing nylon composite materials of this comparative example, are prepared from by the following raw material:
The preparation method of the heat-resisting high flowing nylon composite materials of above-mentioned height, comprises the following steps:
(1) described nylon 6t/11 resin and polyhexamethylene adipamide resin are placed in 90 DEG C, after being dried 5 hours, cooling,
By the nylon 6t/11 resin after cooling, polyhexamethylene adipamide resin, and toluene di-isocyanate(TDI) (tdi), 2,2'- (1,3-
Phenylene)-bisoxazoline (pbo), n, n'- double (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzenedicarboxamide, double (2,6-
Di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-dripping agent (politef) and dimethicone be added to height
Mixed in fast blender；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and n, n'- ethylenebis stearoyl
Amine is added in another homogenizer and is mixed；
(3) compound that step (1) mixes is added in parallel double-screw extruder through feeder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) mixes to be melt extruded, pelletize, technique
Parameter is as follows: area's temperature is 280 DEG C, and two area's temperature are 295 DEG C, and three area's temperature are 300 DEG C, and four area's temperature are 305 DEG C, 5th area
Temperature is 305 DEG C, and six area's temperature are 305 DEG C, and seven area's temperature are 300 DEG C, and eight area's temperature are 300 DEG C, and die head temperature is 300 DEG C,
Screw speed is 300rpm.
The screw configuration of described parallel double-screw extruder is double thread, and the ratio l/d of spiro rod length l and diameter d is 30,
Described screw rod is provided with 2 gear block areas and 1 left-hand thread area.
It is below embodiment and comparative example catalog (table 1):
Table 1 embodiment forms weight portion catalog with comparative example raw material
Above example and the n of comparative example, double (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamide of n'-,
Double (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-dripping agent (politef) and dimethicone
It is respectively 0.15 part, 0.15 part, 1 part, 0.2 part.
The various embodiments described above and comparative example made working of plastics sample are carried out following performance test (result is as shown in table 2):
Mobile performance: by gb/t 3682-2000 standard testing, 309 DEG C of test temperature, load 1.2kg；
Tensile property: by gb/t 1040.1-2006 standard testing, rate of extension 10mm/min；
Heat resistance: by gb/t 1634.1-2004 standard testing, bending stress 0.45mpa；
Water absorbing properties: by gb/t 1034-2008 standard testing, testing time 24h.
Table 2 embodiment and comparative example performance catalog
As can be seen that the addition of amorphous nylon resins (polyhexamethylene adipamide resin) is got over from embodiment 1～6
Many, the melt index of its nylon 6t/11 resin composite materials is bigger, and processing characteristics is better；The addition of alkali-free glass fibre is got over
Many, the tensile strength of its nylon 6t/11 resin composite materials and heat distortion temperature bigger, but produce floating fine probability simultaneously and get over
Greatly；The water absorption rate change of each embodiment is less.Comprehensive factors above, the combination property of embodiment 6 is optimal.
It is compared with embodiment 6, comparative example 1 is to be not added with amorphous nylon resins (polyhexamethylene adipamide resin)
Nylon 6t/11 resin composite materials, its melt index is only 6g/10min (309 DEG C of test temperature, load 1.2kg), processability
Can not be good；Comparative example 2 is to be not added with toluene di-isocyanate(TDI) (tdi), the Buddhist nun of 2,2'- (1,3- phenylene)-bisoxazoline (pbo)
Imperial 6t/11 resin composite materials, amorphous nylon resins (polyhexamethylene adipamide resin) are with nylon 6t/11 resin compatible not
Good, thus bad impact is caused to the tensile property of nylon 6t/11 resin composite materials；Comparative example 3 is to be not added with being coupled
Agent, n, the nylon 6t/11 resin composite materials of n'- ethylenebisstearamide, its nylon 6t/11 resin composite materials surface
Floating fibre phenomenon increases, and resin composite materials are not good with the alkali-free glass fibre compatibility, thus the draftability to resin composite materials
Bad impact can be caused；The screw configuration of the parallel double-screw extruder of comparative example 4 be double thread, spiro rod length l and
The ratio l/d of diameter d be 30, and the screw configuration of the parallel double-screw extruder of embodiment 6 be single thread, spiro rod length l and
The ratio l/d of diameter d is 40, by contrast it is found that being joined using the screw rod of the parallel double-screw extruder described in embodiment 6
Number, the processing characteristics of nylon 6t/11 resin composite materials, tensile property, heat resistance and water absorbing properties that it prepares obtain
Arrive very big improvement, obtain the nylon 6t/11 resin composite materials of high heat-resisting, high fluidity, high tensile and low water absorption
Beneficial effect.
Each technical characteristic of embodiment described above can arbitrarily be combined, for making description succinct, not to above-mentioned reality
The all possible combination of each technical characteristic applied in example is all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all it is considered to be the scope of this specification record.
Embodiment described above only have expressed the several embodiments of the present invention, and its description is more concrete and detailed, but simultaneously
Can not therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
Say, without departing from the inventive concept of the premise, some deformation can also be made and improve, these broadly fall into the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be defined by claims.
Claims (10)
1. a kind of high heat-resisting high flowing nylon composite materials are it is characterised in that be prepared from by the raw material of following weight portion:
The intrinsic viscosity of described nylon 6t/11 resin is 0.7～1.0dl/g；
Described amorphous nylon resins are nylon 46 resin, at least one in polyhexamethylene adipamide resin；
Described coupling agent be gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, n- (β-aminoethyl)-γ-
Aminopropyl triethoxysilane, n- β-(aminoethyl)-γ-aminopropyltrimethoxysilane, n- β-(aminoethyl)-γ-aminopropyl
Methyl dimethoxysilane, γ-aminopropyltriethoxy dimethoxysilane, γ-aminopropyltriethoxy diethoxy silane, anilinomethyl
At least one in triethoxysilane；
The length of described alkali-free glass fibre is 2～4mm, a diameter of 9～11 μm；
Described anti-dripping agent is fluoropolymer.
2. the heat-resisting high flowing nylon composite materials of height according to claim 1 are it is characterised in that former by following weight portion
Material is prepared from:
3. the heat-resisting high flowing nylon composite materials of height according to claim 1 and 2 are it is characterised in that described nylon 6t/11
The intrinsic viscosity of resin is 0.75～0.95dl/g；Described amorphous nylon resins are polyhexamethylene adipamide resin, its characteristic
Viscosity is 1.22～1.84dl/g.
4. the heat-resisting high flowing nylon composite materials of height according to claim 1 and 2 are it is characterised in that described coupling agent is
At least one in gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane；Described anti-dripping agent is polytetrafluoro
Ethylene.
5. the heat-resisting high flowing nylon composite materials of height according to claim 1 and 2 are it is characterised in that described nylon 6t/11
Resin is formed by monomer 1 and polyesteramide copolymerization, described monomer 1 for mol ratio be 1:1:0.45～0.55 hexamethylene diamine, to benzene
Dioctyl phthalate, 11- aminoundecanoic acid, described polyesteramide addition is the 1～8% of described monomer 1 gross weight.
6. the heat-resisting high flowing nylon composite materials of height according to claim 5 are it is characterised in that described nylon 6t/11 tree
Fat is obtained by following synthetic method:
(1) the described monomer 1 after vacuum drying is added in stirring-type polymer reactor, is simultaneously introduced described polyesteramide,
And molecular weight regulator, antioxidant, water；Then evacuation 4～6min, logical nitrogen 4～6min, so circulate 5～7 times, make
Reactant is present in the lower environment of nitrogen protection, control in described stirring-type polymer reactor system pressure for 0.2～
0.3mpa；
(2) in 2～4 hours by airtight for described stirring-type polymer reactor constant-speed heating to 272～280 DEG C, stir described in regulation
The mixing speed mixing formula polymer reactor is 30～50r/min, wherein, when described stirring-type polymer reactor temperature reaches 215
DEG C when, be deflated to 2.0mpa, and maintain pressure in 2.0mpa, after reacting 1～2 hour, be deflated to normal pressure, be warming up to 310 simultaneously
After continuing reaction at～320 DEG C 1～2 hour, constant temperature continued evacuation after 0.3～1 hour, obtained described nylon 6t/11 resin；
Described molecular weight regulator is addition is described monomer 1 gross weight 0.1～3% benzoic acid；Described antioxidant is
Addition is the n of the 0.1～0.3% of described monomer 1 gross weight, n'- bis- (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzene
Diamides；Appropriate amount of water.
7. the preparation method of the heat-resisting high flowing nylon composite materials of the height described in a kind of any one of claim 1-6, its feature exists
In comprising the following steps:
(1) described nylon 6t/11 resin and amorphous nylon resins are placed in 80～100 DEG C, after being dried 4～12 hours, cooling,
By the nylon 6t/11 resin after cooling, amorphous nylon resins, and described toluene di-isocyanate(TDI), 2,2'- (1,3- sub- benzene
Base)-bisoxazoline, n, double (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamide of n'-, double (2,6- di-t-butyl -
4- aminomethyl phenyl) pentaerythritol diphosphate, anti-dripping agent and dimethicone be added in homogenizer and mixed；
(2) by described coupling agent, alkali-free glass fibre and n, n'- ethylenebisstearamide is added to another homogenizer
In mixed；
(3) compound that step (1) mixes is added in parallel double-screw extruder through feeder, and squeeze in parallel double-screw
Go out the mixture that the lateral addition step (2) of machine mixes to be melt extruded, pelletize, technological parameter is as follows: area's temperature is
260～290 DEG C, two area's temperature are 290～305 DEG C, and three area's temperature are 295～310 DEG C, and four area's temperature are 300～310 DEG C, five
Area's temperature be 300～310 DEG C, six area's temperature be 300～310 DEG C, seven area's temperature be 300～310 DEG C, eight area's temperature be 300～
310 DEG C, die head temperature is 295～305 DEG C, and screw speed is 200～600rpm.
8. preparation method according to claim 7 is it is characterised in that by described nylon 6t/11 resin in described step (1)
It is placed in 90 DEG C with amorphous nylon resins, be dried 4～6 hours；Technological parameter in described step (3) is: area's temperature is 260
～285 DEG C, two area's temperature are 290～300 DEG C, and three area's temperature are 295～305 DEG C, and four area's temperature are 300～305 DEG C, five area's temperature
Spend for 300～305 DEG C, six area's temperature are 300～305 DEG C, seven area's temperature are 300～305 DEG C, eight area's temperature are 300～305
DEG C, die head temperature is 295～300 DEG C, and screw speed is 200～400rpm.
9. the preparation method according to claim 7 or 8 is it is characterised in that the screw shaped of described parallel double-screw extruder
Shape is single thread；The ratio l/d of spiro rod length l and diameter d is 35～50；Described screw rod is provided with the gear block area of more than 1
With the left-hand thread area of more than 1.
10. preparation method according to claim 9 is it is characterised in that the ratio l/d of described spiro rod length l and diameter d is 35
～45；Described screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610890231.3A CN106366657B (en) | 2016-10-12 | 2016-10-12 | High heat resistance height flows nylon composite materials and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610890231.3A CN106366657B (en) | 2016-10-12 | 2016-10-12 | High heat resistance height flows nylon composite materials and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106366657A true CN106366657A (en) | 2017-02-01 |
| CN106366657B CN106366657B (en) | 2019-06-14 |
Family
ID=57896430
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610890231.3A Active CN106366657B (en) | 2016-10-12 | 2016-10-12 | High heat resistance height flows nylon composite materials and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106366657B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109553965A (en) * | 2017-09-25 | 2019-04-02 | 北京旭阳科技有限公司 | Nylon composite materials and preparation method thereof |
| CN114316424A (en) * | 2021-11-22 | 2022-04-12 | 金发科技股份有限公司 | Transparent weather-resistant PP/PS composite material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206411A (en) * | 2010-03-30 | 2011-10-05 | E.I.内穆尔杜邦公司 | Flame-retardant polyamide resin composition and products containing same |
| CN103534313A (en) * | 2011-05-13 | 2014-01-22 | 帝斯曼知识产权资产管理有限公司 | Flame retardant semi-aromatic polyamide composition and moulded products made therefrom |
| CN105504789A (en) * | 2014-10-10 | 2016-04-20 | Ems专利股份公司 | Reinforced polyamide moulding compositions and injection mouldings produced therefrom |
-
2016
- 2016-10-12 CN CN201610890231.3A patent/CN106366657B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206411A (en) * | 2010-03-30 | 2011-10-05 | E.I.内穆尔杜邦公司 | Flame-retardant polyamide resin composition and products containing same |
| CN103534313A (en) * | 2011-05-13 | 2014-01-22 | 帝斯曼知识产权资产管理有限公司 | Flame retardant semi-aromatic polyamide composition and moulded products made therefrom |
| CN105504789A (en) * | 2014-10-10 | 2016-04-20 | Ems专利股份公司 | Reinforced polyamide moulding compositions and injection mouldings produced therefrom |
Non-Patent Citations (2)
| Title |
|---|
| 杨鸣波 等: "《中国材料工程大典.第6卷.高分子材料工程（上）》", 31 March 2006, 北京：化学工业出版社 * |
| 汪朝阳 等: "扩链反应在高分子材料合成中的应用", 《化学推进剂与高分子材料》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109553965A (en) * | 2017-09-25 | 2019-04-02 | 北京旭阳科技有限公司 | Nylon composite materials and preparation method thereof |
| CN114316424A (en) * | 2021-11-22 | 2022-04-12 | 金发科技股份有限公司 | Transparent weather-resistant PP/PS composite material and preparation method thereof |
| CN114316424B (en) * | 2021-11-22 | 2023-08-25 | 金发科技股份有限公司 | Transparent weather-proof PP/PS composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106366657B (en) | 2019-06-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106832916B (en) | High heat conductive insulating copolyamide composite material and preparation method | |
| CN106519654B (en) | Halogen-free fire-retarding reinforced polyamide composite material and preparation method | |
| CN106589882A (en) | Polycarbonate and polyketone alloy and preparation method thereof | |
| CN106479174B (en) | Fire-retardant enhancing copolyamide 6T composite material and preparation method | |
| CN106497043B (en) | Fire-retardant enhancing copolyamide composite material and preparation method | |
| CN106519665B (en) | Flame retardancy reinforced polyamide composite material and preparation method thereof | |
| CN106832915B (en) | High heat conductive insulating polyamide 6 T composite material and preparation method | |
| CN107446349A (en) | A kind of ultraviolet aging resistance fire-retardant nylon composite and preparation method thereof | |
| CN109880126A (en) | High-intensitive and heat resistant poly acid imide lightweight labyrinth polyimide precursor gel and its preparation method and application can be prepared | |
| CN106366657A (en) | High-heat-resistance high-flow nylon composite material and preparation method thereof | |
| CN109679341A (en) | A kind of high intensity, high glaze, apperance performance fiberglass reinforced high-temperature nylon material and preparation method thereof | |
| CN106398193B (en) | Heat resistant polyamide 6T/11 composition and preparation method thereof | |
| CN106751800B (en) | Laser direct forming copolyamide 6T composite material and preparation method | |
| CN106433116B (en) | High temperature resistant copolyamide 6T composition and preparation method thereof | |
| CN106633844B (en) | High heat resistance height flows copolyamide 6T composite material and preparation method | |
| CN106519652B (en) | High heat resistance height flows polyamide compoiste material and preparation method thereof | |
| CN106751807B (en) | High heat conductive insulating copolyamide 6T composite material and preparation method | |
| CN106336653B (en) | High temperature resistant co-polyamide composition and preparation method thereof | |
| CN106519664B (en) | High heat resistance height flows copolyamide composite material and preparation method | |
| CN106675020B (en) | Laser direct forming polyamide 6 T composite material and preparation method | |
| CN106433119B (en) | Heat resistant polyamide 10T/11 composition and preparation method thereof | |
| CN114989605B (en) | Polyimide resin with low thermal expansion coefficient and preparation method and application thereof | |
| CN107057341B (en) | High heat conductive insulating polyamide compoiste material and preparation method thereof | |
| CN109897199A (en) | The polyimide precursor gel and its preparation method and application for inhaling wave and heat resistant poly acid imide lightweight labyrinth can be prepared | |
| CN106675012B (en) | Laser direct forming polyamide compoiste material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 523850 Baibugao Avenue, Wushajiang, Chang'an Town, Dongguan City, Guangdong Province, 355 Patentee after: Guangdong Sinoplast New Materials Co.,Ltd. Address before: 523850 Baibugao Avenue, Wushajiang, Chang'an Town, Dongguan City, Guangdong Province, 355 Patentee before: GUANGDONG SINOPLAST ADVANCED MATERIAL CO.,LTD. |
|
| CP01 | Change in the name or title of a patent holder |