JPS60137961A - Manufacture of polyamide composition - Google Patents

Abstract

PURPOSE:To obtain a composition of improved heat and impact resistance and water-absorptivity, with high melt viscosity, by incorporating polyamide with modified aromatic polymer etc. followed by kneading in a molten state. CONSTITUTION:The objective composition can be obtained by incorporating (A) 60-95pts.wt. of a polyamide (pref. polyamide homopolymer) with (B) 5-40pts.wt. of modified aromatic polymer prepared by kneading in a molten state (i) 100pts. wt. of an aromatic polymer (ii) 0.05-5.0pts.wt. of unsaturated compound and (iii) 0.01-5.0pts.wt. of peroxide, and (C) 0-30pts.wt. of either ethylene copolymer or modified ethylene copolymer derived from grafting (iv) 0.05-5.0pts.wt. of unsaturated compound to (v) 100pts.wt. of ethylene copolymer followed by kneading in a molten state. Said unsaturated compound is pref. maleic anhydride, dodecenyl succinie anhydride, etc.

Description

[Detailed description of the invention] The present invention relates to a method for producing polyamide compositions.

For details, improved heat resistance and water absorption.

The present invention relates to a new method for producing polyamide compositions having impact resistance +/1 and high melt viscosity.

Generally, polyamide has a wear resistance of 1<1. Due to its excellent electrical properties and mechanical strength, it is widely used as an engineering resin for various mechanical parts materials, but it lacks sufficient impact resistance and flexibility, has a high water absorption rate, and has an aromatic They have drawbacks such as lower heat resistance than family-based polymers.

In particular, the water absorption rate is quite high, and polyamide that has absorbed water tends to contain air bubbles and whiten when molded, which is undesirable.Moreover, the mechanical strength is extremely low due to water absorption.
: Not only that, but also problems such as dimensional change and deformation occur. Because polyamide has such drawbacks, its use as an engineering/nearing resin is limited, and in many cases it is not possible to take advantage of polyamide's inherently superior properties.

Therefore, to improve the shortcomings of polyamide.

Naturally, the idea of using a polyamide with a polymer having high thermal properties and low water absorption, a good 1tf fx)yR group polymer with 7 degrees of comb elasticity, and a polymer having comb elasticity naturally arises.

However, resin mixtures obtained by mixing polyamide, aromatic polymers, and polymers with rubber elasticity in a conventional manner, or resin compositions obtained by simply melt-kneading them, have poor compatibility. The composition cannot have the desired excellent properties.

The present inventors solved the drawbacks of polyamide by using aromatic polymers.
The present invention was achieved as a result of intensive research aimed at obtaining a resin composition that can be resolved by using a polymer described in L and a polymer having rubber-like elasticity, as the case may be.

That is, the present invention comprises (1) 60 to 95 parts by weight of polyamyl', (2) 100 parts by weight of aromatic polymer, and 0.05 to 5 parts by weight of unsaturated compound.
a modified aromatic polymer obtained by melt-kneading 0 parts by weight and 0.01 to 5.0 parts by weight of peroxide, and

(3) Ethylene copolymerization or ethylene copolymerization 1
Modified ethylene copolymer 0 to 3 obtained by adding 0.05 to 50 parts by weight of an unsaturated compound to 00 parts by weight.
By melting and kneading the 0 weight part. A new method for producing polyamide compositions having improved heat resistance, water absorption, impact resistance and high melt viscosity is provided.

The following is a detailed explanation of the present invention.

Examples of polyamides used in the present invention include nylon 6, nylon/11. Polylactams such as nylon 12 Polyamides obtained from dicarboxylic acids and diamides such as nylon 66, nylon 610, nylon 610, nylon 6/66, nylon 6/61 0
．． Nylon 6/1 2゜Nylon b/b12. Nylon 6/66//) 10° Nylon 76/66/
12 grade copolymerized polyamide stone: Nylo 76/6T (T
semi-aromatic polyamides obtained from aromatic dicarboxylic acids such as inophthalic acid (terenotaric acid component), aromatic dicarboxylic acids such as inophthalic acid, metalloxy/lyle 7/amines, or alicyclic/amino acids.
Polyester amide, polyether amide and polyester amide can be mentioned. It is also possible to use polyamide in combination.

Note that the polyamide that can be used in the present invention is not limited by the type of terminal group, concentration, molecular weight, etc. of the polyamide of JL et al., and various polyamides can be used as long as they are selected from the polyamides mentioned above. I can do it.

It is also possible to use polyamide in which low molecular weight components such as monomers and oligomers that remain or are generated during the combination of polyamides are mixed.

As the polyamide of the present invention, jl'l, German-Chinese combination is used.
Polyamide homopolymers can be said to be preferred components, since the resulting polymer compositions exhibit particularly high heat resistance in these cases.

The aromatic polymer used in the present invention includes:
Polystyrene, styrene-acrylonitrile copolymer +
-J crylonitrile-styreno-butadiene copolymer,
Acrylonitrile-styrene acrylic ester copolymer, methacrylic acid-butadiene 7-styrene copolymer,
Styrenic copolymers such as butadiene-styrene copolymer, chlorinated polyethylene-acrylonitrile-styrene copolymer, polyethylene terephthalate, polybutyne/
Examples include aromatic polyesters such as prephthalates and polyarylates, borinophenol polyphenylene oxides, and improved polyphenylene oxites (noryl resins).

Examples of the unsaturated compounds used in the present invention include α- and β-unsaturated carbonic acids, monoesters and anhydrides thereof, and the like. More specific examples include acrylic acid, tutaacrylic acid, maleic acid, maleinoic acid monomethyl ester, maleic anhydride, itacoaic acid, itaconic acid monomethyl ester, itaconic anhydride, fumaric acid, derivatives thereof, and acids thereof. Metal salts, etc. can be mentioned. Still cycloaliphatic carboxylic acids, more specifically 1-11. Engineering/Tohi/Chlo(2,2,1)-5-hepano-2, Roichicarbo/Acidbuty, 1((Water,/Kuh 4-
/Chlohegysene-1,2-carboxylic acid anhydride, and derivatives thereof, , 11; and metals of these acids 171
1i 2wa can be used. or d, epoxy group-containing compounds, such as glyc/dyl methacrylate.

Various compounds can be used as unsaturated compounds in the present invention.

Furthermore, alkenylcarboxylic acid anhydrides such as dodecenylco-phosphate anhydride, ophtatecenylsuccinic anhydride, 4-methacryloki/ethyltrimellitic anhydride, and derivatives thereof, dicarboxylic acids corresponding to the above acid anhydrides, and mononisters thereof. -Al, metal salts, etc.

1-acryloylbenzotriazole, 1-acryloyl phthalimide 1-acryloyl sulfobenzimide, 1-acryloyl naphthalimide.

Methacryloylbenzotriazole and derivatives thereof can also be used as unsaturated compounds in the present invention.

Preferred unsaturated compounds in the present invention are maleic anhydride, dodecenylconophosphate anhydride, and 1-acryloylbenzotriazole. U) il:,'&:1 + )'J'
di h series hol) Mar 1/CA-J shi 0.05-5.
0 parts by weight, preferably 0.5 to 2.0 parts by weight. If the amount of the unsaturated compound is less than 5 parts by weight, the resulting modified aromatic polymer will have poor compatibility with the polyamide, and even if it is added in an amount greater than 5.0 parts by weight, the effect will be significantly reduced.

The peroxide used in the present invention functions as a reaction initiation catalyst or a crosslinking agent, and examples thereof include ternary butyl hyalochloride, ternary butyl peroxide, and dicumyl peroxide. , hensilver oxide, etc.
An appropriate one is selected from these compounds and used.

The amount of peroxide added is 0.01 to 5.0 parts per 100 parts of aromatic polymer, preferably 0.01 to 5.0 parts.
It is in the range of 1 to 2.0 parts by weight. Added amount of peroxide is 0
．． If the amount is less than 0.01 parts by weight, it will be difficult to function as a reaction initiator. Further, even if more than 5.0 ton Ilt parts is added, there is no change in the reaction initiation catalyst 11.

Denaturation C) Group 6 system Bo 1) -7- & well-known force J, jtt
That's it.

For example, by adding an unsaturated compound and a peroxide to an aromatic polymer,
Produced by melt-kneading at ~30°C.

The ethylene copolymer used in the present invention includes:
First, there may be mentioned a copolymer of ethylene' and a 1/1'' reflexine having 3 or more carbon atoms, or a copolymer of ethylene and an Iz latori I coisodiene.

As the α-olefin with carbon number of 6 or more,
, buf no 1. It is 11 dimensions that can be expressed as γ.
Hexadie/, Pentagene, Synchropentagene,
Methyltetrahytroy/dene, methylenenorbornene,
Examples include ethylidene lua 1(-nene).

In these ethylene copolymers, the content of the ethylene y jli position is 50 to 90 molar, 4? It is preferable that the amount is 50 to 85 mol.
1:l:o, []1 to 10 mol%l especially o,i
~S It is preferable to be in charge of things 1.

The next ethylene copolymer is a copolymer of ethylene and unsaturated carboxylic acid esters [75]. Examples of these include ethylene and
1., End 1) Copolymers with esters selected from the group of methyl methacrylate, ethyl methacrylate, and methyl methacrylate, and ethylene-vinyl acetate polymers can be mentioned. There are no particular restrictions on the content of ester units in the copolymer or the melt/tex of the copolymer, but it is preferable to
Soil: 1, which is a 1-ethylenenoethyl acrylate copolymer
゜Moreover, examples of ethylene copolymers include ethylene,
There are ethylene copolymers made of monomers of unsaturated carboxylic acids, unsaturated funorboxylic acid metal salts, and unsaturated carboxylic acid esters, specifically ethylene ionomer resins.

Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, metal IP of op-zeta metal salts, doshita thorium, nonori-dino 1. Magne/tsul,.

...Riuno 3.1ur-lead etc. are mentioned.

Examples of the unsaturated carboxylic acid ester include ethyl acrylate, methyl acrylate, methacrylic acid ff-r-l, and methyl methacrylate.

The melt intensification of ethylene-based ionomer resin is 7.0 as measured by the method of ASTM-D-1238.
The following are good. Also, what is its embrittlement temperature?

ASTM-D=, -40" as measured by method 746
A rating of C or below is good. In addition, rubbers such as butyl rubber and styrene-butadiene rubber can also be used as ethylene copolymers.

The modified ethylene copolymer of the present invention is obtained by grafting the unsaturated compound onto the ethylene copolymer, and the amount of the unsaturated compound grafted onto the ethylene copolymer is 0.00% relative to the ethylene copolymer. 05 to 5.0 parts by weight,
Preferably it is 0.05 to 2.0 parts by weight. If the amount of the unsaturated compound is less than 0.05 parts by weight, the resulting composition will have poor impact resistance, and if it is more than 5.0 parts by weight, the resulting composition will gel. When producing ethylene copolymers, peroxides are usually used as radical reaction initiators.

The amount of peroxide added is 0.0 per ethylene copolymer.
The amount is 1 to 5.0 parts by weight, preferably 0.1 to 2.0 parts by weight. If the amount of peroxide added is less than 0.01 parts by weight, it will be difficult to function as a reaction initiator.

Furthermore, even if more than 5.0 parts by weight: 1'L is added, there is no change in the reaction initiation effect.

Modified ethylene copolymer was prepared according to a known method.

For example, using one reaction vessel, purified quintessence, an unsaturated compound, and an ethylene copolymer are charged, the temperature is raised to 120'C, and then peroxide dissolved in purified acetone is added dropwise to react. It is produced by adding an unsaturated compound and a peroxide and melt-kneading the mixture at usually 200-350°C, preferably 220-530°C.

Ethylene copolymers can also be made from modified ethylene copolymers.

The ratio of copolymerization of polyamide, modified aromatic polymer, and modified ethylene in the polyamide composition of the present invention is 60 to 95 overlapping parts of polyamide and 5 to 4 parts of modified aromatic polymer.
0 parts by weight, and 0-30 parts by weight of the ethylene copolymer or modified ethylene copolymer. Preferably 60 to 9 parts by weight of polyamide, 10 to 40 parts by weight of modified aromatic polymer
parts by weight, and 0 to 25 parts by weight of the ethylene copolymer or modified ethylene copolymer.

In the polyamide composition of the present invention, if the content of the modified aromatic polymer is less than 5jH1 part, the heat resistance and water absorption of the resulting polyamide composition will be insufficiently improved;
If the amount is more than 0 parts by weight, the resulting composition will have a high melt viscosity and will have poor moldability.

Furthermore, the blending a1- of the ethylene copolymer or modified ethylene copolymer blended to improve the impact resistance is 30
If the amount is greater than 100%, the tensile strength of the resulting composition will decrease and the rate of decrease in heat distortion temperature will increase.

In producing the polyamide composition of the present invention, melt-kneading of the polyamide, modified y; aromatic polymer, and ethylene copolymer or modified ethylene copolymer can be carried out in various conditions.

For example, other components may be added to the polyamide that is still in a molten state after the polymerization reaction is completed and then melt-kneaded.

Alternatively, other components may be added to powdered or pelleted polyamide and melt-kneaded.

The temperature when melting and kneading each component is usually 200 to 200.
°C7 is preferably selected from the range of 240 to 000C. If the melt-blending temperature is lower than 200°C, the raw materials will not be sufficiently melted, making it difficult to completely melt and knead, and if it is lower than 20°C, a decomposition reaction will occur, which is undesirable.

The melt-blending operation for producing the polyamide composition of the present invention can be carried out using a known melt-kneading device such as a twin-screw extruder. Appropriate amounts of stains, old faces, thickening, nucleating agents, fibrous materials, plasticizers, lubricants, blowing agents, heat resistant agents, weathering agents, flame retardants, etc. may be added depending on the situation. The polyamide composite acid obtained by the present invention can be processed into tubes, rods, blow molded products, injection molded products, etc., and can be further added.

It is also possible to perform processing such as painting. or.

It is also an IJ function to use it as an adhesive when manufacturing a compound compound by laminating and bonding a plurality of metal plates. .

Next, Examples and Comparative Examples of the present invention will be described.

In addition, each physical property of the polyamide composition (or mixture) obtained on each side was tested by the following test method.

[Preparation method of test piece]

Test pieces were created by molding the two compositions using a screw line injection molding machine. The cylinder temperature at this time is 250"C
The mold temperature was 80°C.

[Test method for molded products]

1. Izot impact test (with notch) for two types of test pieces, 1 x 2 inch and 1 x 8 inch width ASTM
An Izot impact test (notched) was conducted at 23°C in accordance with the provisions of -D-256. Measured values are in Kqcm
/ It is displayed at cut.

2 Method of measuring water absorption Using a tensile test specimen specified in ASTM-D-6'58, the test specimen was immersed in boiling water at 100°C for 10 hours, and the absolute dryness after molding was measured. ) and the weight after water absorption according to the following formula.

Self-compatibility Compatibility of the composition after melt-kneading was evaluated by a strand bending test. If 9 layer separation, peeling, etc. occur as a result of the strand hJE curve test, mark it as ×.

Those with no change were judged as ○.

4 Heat distortion temperature Heat distortion temperature is in accordance with ASTM-D-6,48.

The song is stress 18. Measured in bKg/-.

5 Melt Index (MI) Melt index was measured under the conditions of temperature 235° C. and load 2.16017′ according to the provisions of ASTM-])-1238. Measured values are shown in Table 75 in units of f/10m1n.
<Sida 4, The raw materials used in the examples and comparative examples are shown below. Polyamide nylon 6 Relative viscosity: 2.80 Amine end group concentration: 8.50 X 10-'e carboxyl end group concentration: 1. 70X 10-' eυ
1 Polystyrene (PS) Styron 666 manufactured by Asahi Kasei 2 Methacrylic acid-styrene copolymer (MS) Cevian-MAS manufactured by Daicel Chemical Industries ■ Polybutylene terephthalate (PBT) Tuffpet-PBT-N1000 manufactured by Mitsubishi Rayon Unsaturated Compound Maleic anhydride (MAR) Peroxide 1 t-Butyl hydroperoxide 11 bottles Barbutyl H made by oil / fat ■ 2 be/silver oxide 1-1 pieces Nipper B made by oil / fat Ethylene copolymer 1 Ethylene-propylene copolymer (tr, prt) Ethylene-ethyl acrylate copolymer (KEA) manufactured by Nippon Synthetic Rubber ■ DPDJ 6169 6 Ethylene-based ionomer resin (I R) Himira 71855 manufactured by Mitsui Polychemical ■ 4 Ethylene-vinyl acetate co-vehicle combination (EVA) manufactured by Ube Industries, Ltd. V 212 Modification example 1 Production of modified PS Borisjire'7 (PS) 100 l'fi i
-1: part and anhydride 7L/inic acid (MAR) 0.5 car: 1:
Part b-Yohi 1. -Zotyl Hydrobar Okey Leeid 0
．． Roshin 1: I part! : 'After blending with a 4-1 filler type mixer, a twin-screw press with a screw diameter of Omm.'
Using a machine/ring temperature 240'C.

Screw rotation speed 40 rplTl + discharge 112Kg/
/hr conditions to melt and knead and pelletize the modified PS.
of,? ! It's I.

Modification Example 2 Production of modified MS Methacrylic acid-styrene copolymer (MS) in place of PS
A modified MS was obtained by carrying out the same experiment as Modification Example 1, except that the cylinder temperature was changed to 2°C.

Production of modified KPR Using a reaction vessel, 62 parts of purified xylene, 100 parts of KPR and 1.5 parts of maleic anhydride (MAR) were charged, and after raising the temperature to 120°C, the mixture was added to purified acetone. Drop 1.1 to 0.7 parts of dissolved benozoyl baroxalyl
The reaction product was recrystallized in acetone under stirring, and unreacted maleic anhydride was removed. In this way, I:I was turned +1mpR
id Malay anhydride/Acid Kraft Wt 1.0 weight: 11° parts)/This 1, Modification Example 4 Production of modified KEA Ethylene-ethyl acrylate copolymer (BKA) 10
0 parts by weight of maleic anhydride, 0,5-m I7' (parts) and 86 parts by weight of t-butyl hydroperoxide O.

After bulleting with a tumbler type mixer, screw diameter 60
Using a 21'1QII extruder with a cylinder/cylinder temperature of 25
0°C, Screw, - Number of revolutions 401”pml Discharge amount 2K
The mixture was melt-kneaded and pelletized under the conditions of 1 g/hr, denatured to give 1 part of male anhydride, 1 part of acid, and a shift ratio of 0.40 parts by weight.

Modification Example 5 Production of modified +1■R In addition to using ethylene ionomer resin (IR) in place of EEA, 1. An experiment similar to Modification Example 4 was conducted.

Modified PBT was obtained by carrying out an experiment similar to Example 1.

Example 1 Modified PS produced in Modification Example 1 with 6.80 parts by weight of nylon
Parts by weight of 2'O were mixed with Triblen I, and the mixture was triblended using a two-piece extruder with a screw diameter of 30 mm.
Pulling temperature: 250'C, screw rotation speed: 100
Melt and knead under the conditions of rpm and discharge rate of 4 Kg/hr,
After converting into pellet I, the obtained pellet was heated at 80°C for 4 hours.
It was dried under reduced pressure for 8 hours.

Next, the pellets were injection molded and their physical properties were determined in four ways.

Example 2 Modified PS with the amount of nylon O used in Example 1 reduced to 70 parts by weight
An example in which the same experiment as in Example 1 was conducted except that the amount used was changed to 60 weight units.
Using modified MS, /su/gu1i1+'r degree is 2
The same experiment as in Example 1 was conducted, except that the temperature was changed to "c".

Example 4 An experiment similar to Example 1 was conducted except that modified PBT produced in Modification Example 6 was used instead of modified PS.

Example 5 The same experiment as in Example 1 was conducted after blending a heavy duty part of nylon 665, 20 parts by weight of modified PS, and 1 part of modified EPR1Si produced by the modified example into a tray.Example 6 In place of modified EPR Modified 1g produced in Modification Example 4 1!
:Δ(Sushi/C et al. conducted an experiment similar to Example 5.

Example 7 The same experiment as in Example 5 was carried out except that the modified IR produced in Modification Example 5 was used in place of the modified (4+ K P R). The same experiment as in Example 5 was conducted except that EEA was used for one cycle.

Example 9 An experiment similar to Example 5 was conducted except that IR was used instead of +1-1]cPR.

Example 10 An experiment similar to Example 5 was conducted except that KVA was used instead of modified EPR.

Comparative Example 1 Injection molding of Nai IJN 6 was carried out to form a product (6 (6 (11)).

Comparative Example 2 680 parts by weight of nylon and 920 parts by weight of unmodified PI were dry-breaded, and the resulting mixture was heated using a screw with a diameter of 30B.
Using a twin-screw pushing machine, / linog temperature 250°C,
Screw rotation speed 10 Orpm + discharge amount 4 Kg/
After melt-kneading and pelletizing under conditions of hr, the obtained pellets were dried under reduced pressure at 80°C for 48 hours.

Next is this beret? , using injection molding, fi thing +1
ill determined.

Ratio 11 school 1 row row nai "Jn 6 envoy] IJ j, i ・70Φ:): Same as comparative example 2 except that the part used was unchanged ('1 ps used company was changed to 30 parts by weight. conducted an experiment.

Comparative Example 4 An experiment similar to Comparative Example 2 was carried out, except that unmodified PIMs were used in place of unmodified PS and the temperature was changed to 2°C.

Comparative Example 5 Unmodified J) In place of S, unmodified 1'11/111 min- was used/(In addition, the same experiment as in Comparative Example 2 was conducted.

- The results of each of the above examples and comparative examples are shown in Table 1.

Claims (3)

[Claims] (1) 60 to 95 parts by weight of polyamide (2) 100 parts by weight of aromatic polymer, 0 unsaturated compounds
．． 05-5.0 parts by weight and peroxide 0.01-5.0
Modified aromatic polymer obtained by melt-kneading parts by weight 5
~40 parts by weight, and. (3) Ethylene copolymer or ethylene copolymer 100
Modified ethylene copolymer obtained by grafting to 05 to 5.0 parts by weight of an unsaturated compound to parts by weight [0 to 60 parts by weight]
I. A method for producing a polyamide composition, which comprises melt-kneading part I.