CN102796258A - Preparation method for in-situ reinforced semi-aromatic polyamide composite material - Google Patents

Preparation method for in-situ reinforced semi-aromatic polyamide composite material Download PDF

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Publication number
CN102796258A
CN102796258A CN2012102596119A CN201210259611A CN102796258A CN 102796258 A CN102796258 A CN 102796258A CN 2012102596119 A CN2012102596119 A CN 2012102596119A CN 201210259611 A CN201210259611 A CN 201210259611A CN 102796258 A CN102796258 A CN 102796258A
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aromatic polyamide
semi
acid
matrix material
preparation
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龙盛如
张美林
杨杰
瞿兰
张刚
王孝军
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Sichuan University
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Sichuan University
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    • 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
    • B29B9/12—Making granules characterised by structure or composition
    • B29B9/14—Making granules characterised by structure or composition fibre-reinforced
    • 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
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/72—Measuring, controlling or regulating
    • 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
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
    • 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
    • B29B9/12—Making granules characterised by structure or composition
    • 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
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04—Particle-shaped
    • 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
    • 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
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92514—Pressure
    • 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
    • B29C2948/9259—Angular 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
    • 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
    • B29C2948/92895—Barrel or housing

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Reinforced Plastic Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a preparation method for an in-situ reinforced semi-aromatic polyamide composite material which is characterized by adding 1000-5000 parts by weight of semi-aromatic polyamide prepolymer, 1-50 parts by weight of a catalyst, 500-5000 parts by weight of a reinforcing fiber and 1-10 parts by weight of a molecular weight conditioning agent into a reaction extruder, and reacting and extruding at the temperature of 290-330 DEG C, under the screw rotating speed of 20-2000 rpm and the vacuum degree of 0.04-0.09 MPa; obtaining the in-situ reinforced semi-aromatic polyamide composite material by pulling, cooling, granulating and drying the extrudate.

Description

A kind of original position strengthens the preparation method of semi-aromatic polyamide matrix material
Technical field
The present invention relates to the preparation method that a kind of original position strengthens the semi-aromatic polyamide matrix material, belong to technical field of polymer materials.
Background technology
Semi-aromatic polyamide is the macromolecular material of one type of high temperature resistant, corrosion-resistant and easy processing, is mainly used in fields such as electronic apparatus and automotive industry.Industrial application often need add fiber and strengthen, like glass fiber reinforced polyester hexamethylene terephthalamide (PA6T) with gather paraphenylene terephthalamide's nonamethylene diamine (PA9T).
Fiber reinforcement semi-aromatic polyamide matrix material mainly adopts virgin resin and fortifying fibre extruding pelletization to obtain at present, but synthetic technology of resins is complicated, and resin is synthetic and the fiber interpolation is separately carried out, and the total energy approach rate is low.Previous work of the present invention openly patent of invention CN102532528A is a raw material with di-carboxylic acid, diamine, nylon salt and amino acid etc.; Elder generation's solid phase polycondensation makes the polymkeric substance of certain molecular weight, extrudes further raising molecular weight through reaction again and obtains the high-molecular weight semi-aromatic polyamide.On this basis, the present invention adopts low-molecular-weight semi-aromatic polyamide performed polymer and fortifying fibre direct reaction to extrude the preparation original position to strengthen the semi-aromatic polyamide matrix material, and the gained matrix material can adopt injection, mold pressing and mode machine-shaping such as extrude.
Summary of the invention
The objective of the invention is to the deficiency of prior art and provide a kind of original position to strengthen the preparation method of semi-aromatic polyamide matrix material; Be characterized in that with the semi-aromatic polyamide performed polymer be raw material; Under the effect of catalyzer and molecular weight regulator; And the adding fortifying fibre, reaction is extruded the preparation original position and is strengthened the semi-aromatic polyamide matrix material.But this method has operate continuously and the high advantage of yield, and the gained matrix material has the processing of being prone to, mechanical strength is high and resistant to elevated temperatures advantage.
The object of the invention is realized that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
Original position strengthens the semi-aromatic polyamide composite material and preparation method thereof and may further comprise the steps:
(1) 1000～5000 parts of semi-aromatic polyamide performed polymers, 1～50 part of catalyzer, 500～5000 parts of fortifying fibres and molecular weight regulator are added extruder for 1～10 part; Under 290～330 ℃ of temperature, screw speed 20～200rpm and vacuum tightness 0.04～0.09MPa, react and extrude, obtain extrudate;
(2) above-mentioned extrudate is obtained original position after traction, cooling, pelletizing and drying and strengthen the semi-aromatic polyamide matrix material.
The structural formula of semi-aromatic polyamide performed polymer is:
Figure BDA00001931146100021
M=2～20 wherein; O＜x+v≤l, at least a among x ≠ O
Figure BDA00001931146100022
Figure BDA00001931146100023
;
R 1=-(CH 2) 2-,-(CH 2) 4-,-(CH 2) 6-,-(CH 2) 9-with---(CH 2) 10-at least a;
R 2=-(CH 2) 4-and/or-(CH 2) 8-;
R 3=-(CH 2) 5-,-(CH 2) 6-,-(CH 2) 7-,-(CH 2) 8-,-(CH 2) 9-,-(CH 2) 10-with-(CH 2) 11-at least a.
Catalyzer is that arriving in phosphoric acid, tetra-sodium, polyphosphoric acid, phosphorous acid, sodium phosphate, Tri sodium Phosphate, sodium phosphite, sodium hypophosphite, propionic acid and the butyric acid lacked a kind of.
Fortifying fibre is at least a in spun glass, thomel, silica fiber, basalt fibre, aramid fiber and the steel fiber.
Molecular weight regulator is phenylformic acid, p-methylbenzoic acid, m-methyl benzoic acid, o-toluic acid, 1-naphthoic acid, 2-naphthoic acid, LAURIC ACID 99 MIN, Palmiticacid, Triple Pressed Stearic Acid, Tetra hydro Phthalic anhydride or 2, any in the 3-dinicotinic acid acid anhydride.
The inlet that adds of semi-aromatic polyamide performed polymer and catalyzer is the main spout of extruder.
The inlet that adds of fortifying fibre is the main spout of extruder and/or auxilliary spout.
The inlet that adds of molecular weight regulator is the auxilliary spout of extruder.
Performance test:
Original position strengthens the semi-aromatic polyamide matrix material and is injected into the standard batten, adopts Tianjin, the island AGS-J of company type electronic universal material testing machine test mechanical property.
The present invention has following advantage:
1. the method that adopts the reaction of semi-aromatic polyamide performed polymer and fortifying fibre to extrude is saved synthetic technology of resins, and the direct production original position strengthens the semi-aromatic polyamide matrix material.
2. the generation of the adding of fortifying fibre and resin is carried out synchronously, and fiber and resin boundary surface are combined, and the mechanical strength of matrix material is high.
3. the kind of semi-aromatic polyamide performed polymer and fortifying fibre is abundant, can produce multiple original position and strengthen the semi-aromatic polyamide matrix material.
4. original position strengthens the preparation method of semi-aromatic polyamide matrix material, reacts the weak point that finds time, and has the advantage of energy-conserving and environment-protective.
5. original position strengthens the preparation method of semi-aromatic polyamide matrix material, and experimental repeatability is good, process stabilizing, and product yield is high.
Embodiment
Through embodiment the present invention is carried out concrete description below; Be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; Can not be interpreted as the restriction to the scope of the present invention includes, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment 1
With the semi-aromatic polyamide performed polymer (by terephthalic acid: the weight ratio preparation of hexanodioic acid: hexanediamine=83:73:116) 5000g and the main spout adding of phosphoric acid 50g from extruder; Spun glass 5000g and phenylformic acid 10g add from auxilliary spout, under 320 ℃ of temperature, screw speed 150rpm and vacuum tightness 0.04MPa, react and extrude; Extrudate obtains original position and strengthens semi-aromatic polyamide matrix material, productive rate 96%, tensile strength 153MPa, flexural strength 248MPa, unnotched impact strength 83kJ/m after traction, cooling, pelletizing and drying 2
Embodiment 2
With semi-aromatic polyamide performed polymer (by the preparation of the weight ratio of terephthalic acid hexanediamine salt: hexanolactam=141:59) 1000g and the main spout adding of tetra-sodium 1g from extruder; Thomel 500g and p-methylbenzoic acid 1g add from auxilliary spout, under 290 ℃ of temperature, screw speed 20rpm and vacuum tightness 0.09MPa, react and extrude; Extrudate obtains original position and strengthens semi-aromatic polyamide matrix material, productive rate 94%, tensile strength 137MPa, flexural strength 241MPa, unnotched impact strength 76kJ/m after traction, cooling, pelletizing and drying 2
Embodiment 3
With the semi-aromatic polyamide performed polymer (by 4; 4 '-(4-thioether phenylformic acid)-triphenylphosphine oxide: decamethylene diamine: the weight ratio preparation of ring oenantholactam=582:172:46) 3500g, polyphosphoric acid 20g and thomel 1000g add from the main spout of extruder; Spun glass 2000g and m-methyl benzoic acid 8g add from auxilliary spout, under 330 ℃ of temperature, screw speed 200rpm and vacuum tightness 0.07MPa, react and extrude; Extrudate obtains original position and strengthens semi-aromatic polyamide matrix material, productive rate 93%, tensile strength 168MPa, flexural strength 257MPa, unnotched impact strength 75kJ/m after traction, cooling, pelletizing and drying 2
Embodiment 4
With semi-aromatic polyamide performed polymer (by the preparation of the weight ratio of m-phthalic acid ethylenediamine salt: nylon salt=120:180) 1500g and the main spout adding of phosphorous acid 10g from extruder; Silica fiber 500g and o-toluic acid 5g add from auxilliary spout, under 300 ℃ of temperature, screw speed 100rpm and vacuum tightness 0.08MPa, react and extrude; Extrudate obtains original position and strengthens semi-aromatic polyamide matrix material, productive rate 91%, tensile strength 94MPa, flexural strength 172MPa, unnotched impact strength 51kJ/m after traction, cooling, pelletizing and drying 2
Embodiment 5
(by the diphenyl sulfide dimethyl chloride: the weight ratio preparation of sebacoyl chloride: tetramethylenediamine=311:358:220) 4000g, sodium phosphate 35g and basalt fibre 1500g add from the main spout of extruder with the semi-aromatic polyamide performed polymer; Basalt fibre 2000g and 1-naphthoic acid 10g add from auxilliary spout, under 310 ℃ of temperature, screw speed 90rpm and vacuum tightness 0.06MPa, react and extrude; Extrudate obtains original position and strengthens semi-aromatic polyamide matrix material, productive rate 92%, tensile strength 149MPa, flexural strength 220MPa, unnotched impact strength 87kJ/m after traction, cooling, pelletizing and drying 2
Embodiment 6
(by the phenyl ether dioctyl phthalate: nonamethylene diamine: the weight ratio preparation of 8-aminocaprylic acid=258:158:84) 2000g and Tri sodium Phosphate 5g, sodium phosphate 10g are from the main spout adding of extruder with the semi-aromatic polyamide performed polymer; Aramid fiber 1000g and 2-naphthoic acid 3g add from auxilliary spout, under 300 ℃ of temperature, screw speed 60rpm and vacuum tightness 0.09MPa, react and extrude; Extrudate obtains original position and strengthens semi-aromatic polyamide matrix material, productive rate 95%, tensile strength 128MPa, flexural strength 213MPa, unnotched impact strength 78kJ/m after traction, cooling, pelletizing and drying 2
Embodiment 7
(by benzophenone dicarboxylic acid: the weight ratio preparation of decamethylene diamine: 9 aminononanoic acid: hexanolactam=270:172:158:50) 3500g, sodium phosphite 35g and spun glass 2000g add from the main spout of extruder with the semi-aromatic polyamide performed polymer; Steel fiber 100g and LAURIC ACID 99 MIN 8g add from auxilliary spout, under 305 ℃ of temperature, screw speed 120rpm and vacuum tightness 0.08MPa, react and extrude; Extrudate obtains original position and strengthens semi-aromatic polyamide matrix material, productive rate 93%, tensile strength 178MPa, flexural strength 260MPa, unnotched impact strength 95kJ/m after traction, cooling, pelletizing and drying 2
Embodiment 8
With the semi-aromatic polyamide performed polymer (by the sulfobenzide dioctyl phthalate: the weight ratio preparation of the amino capric acid=306:30:53:334 of quadrol: hexanediamine: 10-) 3200g and the main spout adding of sodium hypophosphite 30g from extruder; Spun glass 1800g and Palmiticacid 7g add from auxilliary spout, under 325 ℃ of temperature, screw speed 170rpm and vacuum tightness 0.09MPa, react and extrude; Extrudate obtains original position and strengthens semi-aromatic polyamide matrix material, productive rate 93%, tensile strength 167MPa, flexural strength 232MPa, unnotched impact strength 82kJ/m after traction, cooling, pelletizing and drying 2
Embodiment 9
With the semi-aromatic polyamide performed polymer (by 4; 4 '-(4-thioether phenylformic acid)-UVNUL MS-40: the weight ratio preparation of the amino hendecoic acid=243:44:163 of tetramethylenediamine: 11-) 4500g and propionic acid 40g add from the main spout of extruder; Spun glass 2500g and Triple Pressed Stearic Acid 10g add from auxilliary spout, under 320 ℃ of temperature, screw speed 160rpm and vacuum tightness 0.05MPa, react and extrude; Extrudate obtains original position and strengthens semi-aromatic polyamide matrix material, productive rate 92%, tensile strength 123MPa, flexural strength 216MPa, unnotched impact strength 75kJ/m after traction, cooling, pelletizing and drying 2
Embodiment 10
With the semi-aromatic polyamide performed polymer (by 4; 4 '-(4-thioether phenylformic acid)-sulfobenzide: 4; 4 '-(4-thioether phenylformic acid)-UVNUL MS-40: the weight ratio preparation of hexanodioic acid: hexanediamine=26:219:146:174) 2400g and butyric acid 20g add from the main spout of extruder; Steel fiber 500g and Tetra hydro Phthalic anhydride 6g add from auxilliary spout, under 295 ℃ of temperature, screw speed 70rpm and vacuum tightness 0.07MPa, react and extrude; Extrudate obtains original position and strengthens semi-aromatic polyamide matrix material, productive rate 94%, tensile strength 94MPa, flexural strength 187MPa, unnotched impact strength 53kJ/m after traction, cooling, pelletizing and drying 2
Embodiment 11
With the semi-aromatic polyamide performed polymer (by 4; 4 '-(4-oxybenzoic acid)-UVNUL MS-40: the weight ratio preparation of sebacic acid: decamethylene diamine=227:101:172) 3900g, phosphoric acid 20g and polyphosphoric acid 15g add from the main spout of extruder; Thomel 2600g and 2; 3-dinicotinic acid acid anhydride 7g adds from auxilliary spout, under 330 ℃ of temperature, screw speed 150rpm and vacuum tightness 0.07MPa, reacts and extrudes; Extrudate obtains original position and strengthens semi-aromatic polyamide matrix material, productive rate 95%, tensile strength 164MPa, flexural strength 239MPa, unnotched impact strength 86kJ/m after traction, cooling, pelletizing and drying 2
Embodiment 12
With the semi-aromatic polyamide performed polymer (by 4; 4 '-(4-oxybenzoic acid)-sulfobenzide: the weight ratio preparation of hexanodioic acid: nonamethylene diamine=245:73:158) 4800g, Tri sodium Phosphate 47g and silica fiber 1200g add from the main spout of extruder; Spun glass 2500g and o-toluic acid 10g add from auxilliary spout, under 325 ℃ of temperature, screw speed 170rpm and vacuum tightness 0.08MPa, react and extrude; Extrudate obtains original position and strengthens semi-aromatic polyamide matrix material, productive rate 91%, tensile strength 171MPa, flexural strength 268MPa, unnotched impact strength 77kJ/m after traction, cooling, pelletizing and drying 2
Embodiment 13
(by the triphenylphosphine oxide dioctyl phthalate: the weight ratio preparation of decamethylene diamine: hexanolactam=183:86:81) 3400g, phosphorous acid 35g and basalt fibre 2100g add from the main spout of extruder with the semi-aromatic polyamide performed polymer; Steel fiber 500g and 2-naphthoic acid 7g add from auxilliary spout, under 320 ℃ of temperature, screw speed 100rpm and vacuum tightness 0.06MPa, react and extrude; Extrudate obtains original position and strengthens semi-aromatic polyamide matrix material, productive rate 94%, tensile strength 137MPa, flexural strength 249MPa, unnotched impact strength 62kJ/m after traction, cooling, pelletizing and drying 2
Embodiment 14
With the semi-aromatic polyamide performed polymer (by 4; 4 '-(4-oxybenzoic acid)-triphenylphosphine oxide: tetramethylenediamine: the weight ratio preparation of ring oenantholactam=275:44:171) 2700g, propionic acid 8g, phosphoric acid 20g and spun glass 1500g add from the main spout of extruder; Thomel 800g and phenylformic acid 8g add from auxilliary spout, under 315 ℃ of temperature, screw speed 140rpm and vacuum tightness 0.05MPa, react and extrude; Extrudate obtains original position and strengthens semi-aromatic polyamide matrix material, productive rate 92%, tensile strength 173MPa, flexural strength 266MPa, unnotched impact strength 84kJ/m after traction, cooling, pelletizing and drying 2
Embodiment 15
(by terephthalic acid hexanediamine salt: the weight ratio preparation of nylon salt: hexanolactam=846:524:113) 2100g, sodium phosphite 18g and silica fiber 800g add from the main spout of extruder with the semi-aromatic polyamide performed polymer; Basalt fibre 1200g and Triple Pressed Stearic Acid 5g add from auxilliary spout, under 310 ℃ of temperature, screw speed 160rpm and vacuum tightness 0.06MPa, react and extrude; Extrudate obtains original position and strengthens semi-aromatic polyamide matrix material, productive rate 95%, tensile strength 158MPa, flexural strength 243MPa, unnotched impact strength 76kJ/m after traction, cooling, pelletizing and drying 2

Claims (8)

1. an original position strengthens the preparation method of semi-aromatic polyamide matrix material, it is characterized in that this method may further comprise the steps:
(1) by weight; 1000～5000 parts of semi-aromatic polyamide performed polymers, 1～50 part of catalyzer, 500～5000 parts of fortifying fibres and molecular weight regulator are added extruder for 1～10 part; Under 290～330 ℃ of temperature, screw speed 20～200rpm and vacuum tightness 0.04～0.09MPa, react and extrude, obtain extrudate;
(2) above-mentioned extrudate is obtained original position after traction, cooling, pelletizing and drying and strengthen the semi-aromatic polyamide matrix material.
2. strengthen the preparation method of semi-aromatic polyamide matrix material according to the said original position of claim 1, it is characterized in that the structural formula of semi-aromatic polyamide performed polymer is:
Figure FDA00001931146000011
M=2～20 wherein; 0＜x+y≤1, at least a in x ≠ 0 ;
R 1=-(CH 2) 2-,-(CH 2) 4-,-(CH 2) 6-,-(CH 2) 9-with-(CH 2) 10-at least a;
R 2=-(CH 2) 4-and/or-(CH 2) 8-;
R 3=-(CH 2) 5-,-(CH 2) 6-,-(CH 2) 7-,-(CH 2) 8-,-(CH 2) 9-,-(CH 2) 10-with-(CH 2) 11-at least a.
3. strengthen the preparation method of semi-aromatic polyamide matrix material according to the said original position of claim 1, it is characterized in that catalyzer is at least a in phosphoric acid, tetra-sodium, polyphosphoric acid, phosphorous acid, sodium phosphate, Tri sodium Phosphate, sodium phosphite, sodium hypophosphite, propionic acid and the butyric acid.
4. strengthen the preparation method of semi-aromatic polyamide matrix material according to the said original position of claim 1, it is characterized in that fortifying fibre is at least a in spun glass, thomel, silica fiber, basalt fibre, aramid fiber and the steel fiber.
5. strengthen the preparation method of semi-aromatic polyamide matrix material according to the said original position of claim 1; It is characterized in that molecular weight regulator is phenylformic acid, p-methylbenzoic acid, m-methyl benzoic acid, o-toluic acid, 1-naphthoic acid, 2-naphthoic acid, LAURIC ACID 99 MIN, Palmiticacid, Triple Pressed Stearic Acid, Tetra hydro Phthalic anhydride or 2, any in the 3-dinicotinic acid acid anhydride.
6. strengthen the preparation method of semi-aromatic polyamide matrix material according to claim 1 or 2 or 3 said original positions, it is characterized in that the inlet that adds of semi-aromatic polyamide performed polymer and catalyzer is the main spout of extruder.
7. strengthen the preparation method of semi-aromatic polyamide matrix material according to claim 1 or 4 said original positions, it is characterized in that the inlet that adds of fortifying fibre is the main spout of extruder and/or auxilliary spout.
8. strengthen the preparation method of semi-aromatic polyamide matrix material according to claim 1 or 5 said original positions, it is characterized in that the inlet that adds of molecular weight regulator is the auxilliary spout of extruder.
CN2012102596119A 2012-07-25 2012-07-25 Preparation method for in-situ reinforced semi-aromatic polyamide composite material Pending CN102796258A (en)

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CN103044911A (en) * 2012-12-21 2013-04-17 湖北工业大学 Nylon 6/plant fiber composite material and preparation method thereof
CN104109236A (en) * 2014-07-21 2014-10-22 四川大学 Fatty cyclosemi aromatic polyarylether amide and preparation method thereof

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CN1166843A (en) * 1995-10-27 1997-12-03 三井石油化学工业株式会社 Semiaromatic polyamide, process for producing the same, and composition containing the same
CN1590461A (en) * 2003-08-05 2005-03-09 阿托菲纳公司 Semi-aromatic polyamides with low moisture regain
CN102532528A (en) * 2012-02-10 2012-07-04 四川大学 Method for preparing semi-aromatic polyamide

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CN1166843A (en) * 1995-10-27 1997-12-03 三井石油化学工业株式会社 Semiaromatic polyamide, process for producing the same, and composition containing the same
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CN103044911A (en) * 2012-12-21 2013-04-17 湖北工业大学 Nylon 6/plant fiber composite material and preparation method thereof
CN104109236A (en) * 2014-07-21 2014-10-22 四川大学 Fatty cyclosemi aromatic polyarylether amide and preparation method thereof
CN104109236B (en) * 2014-07-21 2016-04-06 四川大学 Fatty ring half aromatics polyarylether amide and preparation method thereof

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Application publication date: 20121128