CN102786795A - Preparation method for in situ filled semi-aromatic polyamide composite material - Google Patents
Preparation method for in situ filled semi-aromatic polyamide composite material Download PDFInfo
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- CN102786795A CN102786795A CN2012102601719A CN201210260171A CN102786795A CN 102786795 A CN102786795 A CN 102786795A CN 2012102601719 A CN2012102601719 A CN 2012102601719A CN 201210260171 A CN201210260171 A CN 201210260171A CN 102786795 A CN102786795 A CN 102786795A
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Abstract
The invention discloses a preparation method for an in situ filled semi-aromatic polyamide composite material. The method is characterized by comprising the following steps: adding 1000 to 5000 parts by weight of a semi-aromatic polyamide prepolymer, 1 to 50 parts by weight of a catalyst, 10 to 5000 parts by weight of a filling material and 1 to 10 parts by weight of a molecular weight regulator into a reaction extruder; carrying out reactive extrusion under the conditions of a temperature of 290 to 330 DEG C, a screw rotation speed of 20 to 200 rpm and a vacuum degree of 0.04 to 0.09 MPa; and then carrying out traction, cooling, granulation and drying on obtained extrudate so as to obtain the in situ filled semi-aromatic polyamide composite material.
Description
Technical field
The present invention relates to a kind of original position and fill the preparation method of semi-aromatic polyamide matrix material, belong to technical field of polymer materials.
Background technology
The semi-aromatic polyamide matrix material has good thermotolerance and mechanical property, is widely used in fields such as electronic apparatus and automotive industry.Simultaneously, in order to expand its application, need in the semi-aromatic polyamide resin, add filler usually and obtain the functionalization matrix material at conduction, heat conduction and aspect such as wear-resisting.
At present functionalization semi-aromatic polyamide matrix material mainly adopts virgin resin and filler extruding pelletization to make, but synthetic technology of resins is complicated, and resin synthesizes and the blend process in will be through twice granulation, energy consumption is higher.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 filler direct reaction to extrude the preparation original position and fills the semi-aromatic polyamide matrix material, and this 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 fill 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 with the filler blend, reaction is extruded the preparation original position and is filled the semi-aromatic polyamide matrix material.But this method has operate continuously and the high advantage of yield, and 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 is filled the semi-aromatic polyamide composite material and preparation method thereof and may further comprise the steps:
(1) by weight; 1000～5000 parts of semi-aromatic polyamide performed polymers, 1～50 part of catalyzer, 10～5000 parts of fillers 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 fill the semi-aromatic polyamide matrix material.
The structural formula of semi-aromatic polyamide performed polymer is:
M=2～20,0＜x+y≤1 wherein, x ≠ 0
Ar =
at least one of;
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 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.
Filler is at least a in lime carbonate, silicon-dioxide, titanium oxide, zinc oxide, polynite, kaolin, glass microballon, graphite, carbon black, carbon nanotube, aluminium nitride AlN, SP 1, Marinco H, white lake, ammonium polyphosphate, trimeric cyanamide and the molybdenumdisulphide.
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.
Performance test:
Original position is filled 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 filler to extrude is saved synthetic technology of resins, and the direct production original position is filled the semi-aromatic polyamide matrix material.
2. the generation of the adding of filler and semiaromatic polyamides resin is carried out synchronously, and filler and resin boundary surface are combined, and mechanics of composites intensity is high.
3. the kind of semi-aromatic polyamide performed polymer and filler is abundant, can produce multiple original position and fill the semi-aromatic polyamide matrix material.
4. original position is filled 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 is filled 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
(by terephthalic acid: the weight ratio preparation of hexanodioic acid: hexanediamine=83:73:116) 5000g, phosphoric acid 50g, lime carbonate 5000g and phenylformic acid 10g add extruder, under 315 ℃ of temperature, screw speed 130rpm and vacuum tightness 0.07MPa, react and extrude with the semi-aromatic polyamide performed polymer; Extrudate obtains original position and fills semi-aromatic polyamide matrix material, productive rate 93%, tensile strength 97MPa, flexural strength 219MPa, unnotched impact strength 54kJ/m after traction, cooling, pelletizing and drying
2
Embodiment 2
Semi-aromatic polyamide performed polymer (by the weight ratio preparation of terephthalic acid hexanediamine salt: hexanolactam=141:59) 1000g, tetra-sodium 1g, silica 1 0g and p-methylbenzoic acid 1g are added extruder, under 330 ℃ of temperature, screw speed 20rpm and vacuum tightness 0.08MPa, react and extrude; Extrudate obtains original position and fills semi-aromatic polyamide matrix material, productive rate 95%, tensile strength 82MPa, flexural strength 180MPa, unnotched impact strength 67kJ/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) 4000g, polyphosphoric acid 35g, silica 1 5g, titanium oxide 70g and m-methyl benzoic acid 7g add extruder, under 290 ℃ of temperature, screw speed 200rpm and vacuum tightness 0.09MPa, react and extrude; Extrudate obtains original position and fills semi-aromatic polyamide matrix material, productive rate 92%, tensile strength 88MPa, flexural strength 191MPa, unnotched impact strength 55kJ/m after traction, cooling, pelletizing and drying
2
Embodiment 4
Semi-aromatic polyamide performed polymer (by the weight ratio preparation of m-phthalic acid ethylenediamine salt: nylon salt=120:180) 3400g, phosphorous acid 15g, zinc oxide 2700g and o-toluic acid 5g are added extruder, under 310 ℃ of temperature, screw speed 120rpm and vacuum tightness 0.04MPa, react and extrude; Extrudate obtains original position and fills semi-aromatic polyamide matrix material, productive rate 94%, tensile strength 109MPa, flexural strength 233MPa, unnotched impact strength 39kJ/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) 2100g, sodium phosphate 43g, polynite 50g, kaolin 1200g and 1-naphthoic acid 3g add extruder, under 300 ℃ of temperature, screw speed 85rpm and vacuum tightness 0.06MPa, react and extrude with the semi-aromatic polyamide performed polymer; Extrudate obtains original position and fills semi-aromatic polyamide matrix material, productive rate 95%, tensile strength 92MPa, flexural strength 195MPa, unnotched impact strength 51kJ/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) 3000g, Tri sodium Phosphate 25g, glass microballon 700g and 2-naphthoic acid 9g add extruder, under 320 ℃ of temperature, screw speed 100rpm and vacuum tightness 0.08MPa, react and extrude with the semi-aromatic polyamide performed polymer; Extrudate obtains original position and fills semi-aromatic polyamide matrix material, productive rate 94%, tensile strength 91MPa, flexural strength 206MPa, unnotched impact strength 42kJ/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) 4300g, sodium phosphite 36g, graphite 1000g, aluminium nitride AlN 200g and LAURIC ACID 99 MIN 10g add extruder, under 325 ℃ of temperature, screw speed 140rpm and vacuum tightness 0.05MPa, react and extrude with the semi-aromatic polyamide performed polymer; Extrudate obtains original position and fills semi-aromatic polyamide matrix material, productive rate 91%, tensile strength 87MPa, flexural strength 192MPa, unnotched impact strength 45kJ/m after traction, cooling, pelletizing and drying
2
Embodiment 8
(by the sulfobenzide dioctyl phthalate: the weight ratio preparation of the amino capric acid=306:30:53:334 of quadrol: hexanediamine: 10-) 3700g, sodium hypophosphite 35g, carbon nanotube 50g, SP 1 950 and Palmiticacid 7g add extruder, under 315 ℃ of temperature, screw speed 125rpm and vacuum tightness 0.07MPa, react and extrude with the semi-aromatic polyamide performed polymer; Extrudate obtains original position and fills semi-aromatic polyamide matrix material, productive rate 92%, tensile strength 94MPa, flexural strength 203MPa, unnotched impact strength 38kJ/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-) 1700g, propionic acid 14g, carbon black 550g and Triple Pressed Stearic Acid 6g add extruder, under 295 ℃ of temperature, screw speed 180rpm and vacuum tightness 0.07MPa, react and extrude; Extrudate obtains original position and fills semi-aromatic polyamide matrix material, productive rate 93%, tensile strength 81MPa, flexural strength 176MPa, unnotched impact strength 39kJ/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) 4800g, Tri sodium Phosphate 45g, Marinco H 1200g, white lake 1500g and Tetra hydro Phthalic anhydride 9g add extruder, under 300 ℃ of temperature, screw speed 100rpm and vacuum tightness 0.06MPa, react and extrude; Extrudate obtains original position and fills semi-aromatic polyamide matrix material, productive rate 94%, tensile strength 85MPa, flexural strength 187MPa, unnotched impact strength 52kJ/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) 3600g, butyric acid 25g, ammonium polyphosphate 200g, trimeric cyanamide 50g and 2; 3-dinicotinic acid acid anhydride 5g adds extruder, under 310 ℃ of temperature, screw speed 90rpm and vacuum tightness 0.09MPa, reacts and extrudes; Extrudate obtains original position and fills semi-aromatic polyamide matrix material, productive rate 95%, tensile strength 96MPa, flexural strength 211MPa, unnotched impact strength 67kJ/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) 2800g, polyphosphoric acid 42g, graphite 200g, molybdenumdisulphide 60g and p-methylbenzoic acid 8g add extruder, under 305 ℃ of temperature, screw speed 110rpm and vacuum tightness 0.07MPa, react and extrude; Extrudate obtains original position and fills semi-aromatic polyamide matrix material, productive rate 92%, tensile strength 88MPa, flexural strength 194MPa, unnotched impact strength 54kJ/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) 3200g, sodium phosphate 20g, Tri sodium Phosphate 10g, polynite 100g and phenylformic acid 6g add extruder, under 310 ℃ of temperature, screw speed 80rpm and vacuum tightness 0.08MPa, react and extrude with the semi-aromatic polyamide performed polymer; Extrudate obtains original position and fills semi-aromatic polyamide matrix material, productive rate 92%, tensile strength 73MPa, flexural strength 154MPa, unnotched impact strength 51kJ/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) 4100g, tetra-sodium 15g, propionic acid 10g, silica 1 000g and 1-naphthoic acid 10g add extruder, under 290 ℃ of temperature, screw speed 160rpm and vacuum tightness 0.09MPa, react and extrude; Extrudate obtains original position and fills semi-aromatic polyamide matrix material, productive rate 93%, tensile strength 69MPa, flexural strength 158MPa, unnotched impact strength 47kJ/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) 3700g, polyphosphoric acid 33g, lime carbonate 1500g, silicon-dioxide 500g and Palmiticacid 8g add extruder, under 310 ℃ of temperature, screw speed 130rpm and vacuum tightness 0.07MPa, react and extrude with the semi-aromatic polyamide performed polymer; Extrudate obtains original position and fills semi-aromatic polyamide matrix material, productive rate 94%, tensile strength 78MPa, flexural strength 185MPa, unnotched impact strength 59kJ/m after traction, cooling, pelletizing and drying
2
Claims (5)
1. an original position is filled 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, 10～5000 parts of fillers 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 fill the semi-aromatic polyamide matrix material.
2. fill 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:
M=2～20,0＜x+y≤1 wherein, x ≠ 0
Ar =
is at least one;
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. fill 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. fill the preparation method of semi-aromatic polyamide matrix material according to the said original position of claim 1, it is characterized in that filler is at least a in lime carbonate, silicon-dioxide, titanium oxide, zinc oxide, polynite, kaolin, glass microballon, graphite, carbon black, carbon nanotube, aluminium nitride AlN, SP 1, Marinco H, white lake, ammonium polyphosphate, trimeric cyanamide and the molybdenumdisulphide.
5. fill 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.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105295029A (en) * | 2015-12-04 | 2016-02-03 | 黄淮学院 | Nano zinc oxide and polyamide composite and preparation method thereof |
| CN106750271A (en) * | 2016-11-23 | 2017-05-31 | 广东聚航新材料研究院有限公司 | The preparation method of nano silicon reinforced nylon 6 composite |
| CN109023585A (en) * | 2018-08-03 | 2018-12-18 | 巢湖市渔郎渔具有限公司 | A kind of antibiotic cleaning fishing net and preparation method thereof |
| PL423772A1 (en) * | 2017-12-07 | 2019-06-17 | Grupa Azoty Spółka Akcyjna | Method for obtaining polyphthalamide composites with silica nanofiller |
| US11505649B2 (en) | 2017-09-28 | 2022-11-22 | Dupont Polymers, Inc. | Polymerization process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1346378A (en) * | 1999-03-22 | 2002-04-24 | Dsm有限公司 | Process for the preparation of polyamide granules |
| JP2009114429A (en) * | 2007-10-19 | 2009-05-28 | Toray Ind Inc | Continuous production method of polyamide |
| CN102532528A (en) * | 2012-02-10 | 2012-07-04 | 四川大学 | Method for preparing semi-aromatic polyamide |
-
2012
- 2012-07-25 CN CN2012102601719A patent/CN102786795A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1346378A (en) * | 1999-03-22 | 2002-04-24 | Dsm有限公司 | Process for the preparation of polyamide granules |
| JP2009114429A (en) * | 2007-10-19 | 2009-05-28 | Toray Ind Inc | Continuous production method of polyamide |
| CN102532528A (en) * | 2012-02-10 | 2012-07-04 | 四川大学 | Method for preparing semi-aromatic polyamide |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105295029A (en) * | 2015-12-04 | 2016-02-03 | 黄淮学院 | Nano zinc oxide and polyamide composite and preparation method thereof |
| CN106750271A (en) * | 2016-11-23 | 2017-05-31 | 广东聚航新材料研究院有限公司 | The preparation method of nano silicon reinforced nylon 6 composite |
| US11505649B2 (en) | 2017-09-28 | 2022-11-22 | Dupont Polymers, Inc. | Polymerization process |
| PL423772A1 (en) * | 2017-12-07 | 2019-06-17 | Grupa Azoty Spółka Akcyjna | Method for obtaining polyphthalamide composites with silica nanofiller |
| CN109023585A (en) * | 2018-08-03 | 2018-12-18 | 巢湖市渔郎渔具有限公司 | A kind of antibiotic cleaning fishing net and preparation method thereof |
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Application publication date: 20121121 |