JPS63275663A - Production of crosslinked resin - Google Patents

Abstract

PURPOSE:To obtain a crosslinked resin having excellent heat resistance, chemical resistance and mechanical properties, by a rapid crosslinking reaction wherein a compsn. comprising a thermoplastic resin and a particular polyoxazine deriv. is heated in the presence of a catalyst. CONSTITUTION:A thermoplastic resin (i) (e.g., polycarbonate obtd. by transesterification between bisphenol A and diphenyl carbonate) pref. having a glass transition temp. of 50 deg.C or above and an intrinsic viscosity of at least 0.3 is mixed with a polyoxazine deriv. (ii) of the formula (wherein n is 2-4; R is an n-valent aliph., alicyclic or arom. hydrocarbon residue, provided that when n is 2, R may be a direct bond; and Ra-f is H, a 3C or lower aliph. hydrocarbon residue, or a 7C or lower arom. hydrocarbon residue) in a wt. ratio of i to ii of 90-30/10-70, thereby obtaining a compsn. This compsn. is heated in the presence of a catalyst (I) amounting to 0.01-20mol.% per mol. of the component (ii) by heating at 160 deg.C or above for 10sec-60min, pref. in a mold.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a method for producing a crosslinked resin, and more specifically, the present invention relates to a method for producing a crosslinked resin. The present invention relates to a method for producing the product with high flexibility and excellent moldability.

<Prior Art> In recent years, with the advancement of technology, there has been a demand for resins that have excellent heat resistance, mechanical properties, and moldability. Among these resins, reaction-molding resins using reactive monomers or oligomers, that is, resins in which molding and polymerization are simultaneously performed using raw materials with relatively low viscosity, have attracted particular attention. Such resins include polyurethane resin and polyurea resin.

Nylon resins, epoxy resins, unsaturated polyester resins, etc. are known, and some are commercialized.

However, each of these resins has its advantages and disadvantages.
For example, polyurethane resins have low heat resistance, and unsaturated polyester resins have drawbacks such as the time required for reaction, that is, molding, and cannot necessarily be said to have sufficient performance and moldability.

On the other hand, thermoplastic resins such as aromatic polyester, aromatic polycarbonate, and polyamide are known as polymers that can be melt molded and have excellent mechanical properties. However, such thermoplastic resins do not have sufficient heat resistance compared to thermosetting resins, and also have problems in chemical resistance.

<Purpose of the Invention> The present inventors have developed a new resin that combines the excellent moldability and mechanical properties of thermoplastic resins with the excellent heat resistance, chemical resistance, etc. of thermosetting resins. As a result of intensive study, we found that by heating a composition formed by blending a thermoplastic resin and a polyoxazine derivative in a specific ratio in the presence of a catalyst, and polymerizing the polyoxazine derivative in the thermoplastic resin matrix, It was discovered that a strong crosslinked resin having the above-mentioned properties could be obtained, and the present invention was achieved.

Therefore, an object of the present invention is to provide a method for producing a crosslinked resin having excellent heat resistance, chemical resistance, and mechanical properties quickly and with excellent moldability.

<Configuration/Effects of the Invention> According to the present invention, an object of the present invention is to provide thermoplastic resin (A)
and a polyoxazine derivative (B) represented by the following formula (I) a -C-Rh / \ Rc -C-Re f , and the ratio of the thermoplastic resin (A) to the polyoxazine derivative (B) is the same by weight. A composition having a ratio of 90:10 to 30 near 0,
This is achieved by a method for producing a crosslinked resin characterized by carrying out a heating reaction in the presence of a catalyst.

The thermoplastic resin used as component A in the present invention includes aromatic polyester and polyamide.

Examples include aromatic polycarbonates, polysulfones, polyethers, polyethersulfones, polyetherimides, polyolefins, acrylic resins, etc. Among these, those with a glass transition point ('1' g ) of 50°C
This glass transition point (Tg) is preferably higher than or equal to
The higher the temperature, the higher the heat resistance of the resulting crosslinked resin, so those with a glass transition point (Tg) of 100°C or higher are more preferable.Specific examples of preferable thermoplastic resins include aromatic polycarbonate, polyarylate, and polyester. Examples include non-quality or poorly crystalline polymers such as etherimide, polysulfone, and polyethersulfone.

The degree of polymerization of thermoplastic resin is, for example, 0.0 in terms of intrinsic viscosity.
It is preferably 3 or more, more preferably 0.4 or more, particularly 0.5 or more.

The polyoxazine derivative used as component B in the present invention is a compound represented by the following formula (■)) a N-C-Rb7\Rc0-C-Ref. In the above formula, n represents an integer of 2 to 4, with 2 being preferred.

R represents an n-valent aliphatic, alicyclic, or aromatic hydrocarbon group, and when n = 2, R may be a direct bond, R
Specifically, when n=2, ethylene, trimethylene, propylene, tetramethylene, hexamethylene, neobenzene, aliphatic group having 10 or less carbon atoms, alicyclic group having 10 or less carbon atoms, aromatic group having 12 carbon atoms or less Hydrocarbon groups are preferred.

Ra, Rb, Rc, Rd, Re and Rf each represent a hydrogen atom, an aliphatic hydrocarbon group having 3 or less carbon atoms, and an aromatic hydrocarbon group having 7 or less carbon atoms, and these may be the same or different, Specifically, examples of the aliphatic hydrogen group having 3 or less carbon atoms include methyl group and ethyl group, and examples of the aromatic hydrocarbon group having 7 or less carbon atoms include phenyl group and tolyl group. Ra, Rb, Re, Rd,
It is preferable that all of Re and Rf are hydrogen atoms, or any one of them is a methyl group, and the rest are hydrogen atoms, and it is particularly preferable that all of them are hydrogen atoms.

Specifically, such polyoxazine derivatives include 2
, 2°-bis(5,6-sihydro-40-1,3-oxazine), 2,2'-ethylenebis(5,6-sihydro-48-1,3-oxazine), 2,2'-tetramethylenebis (5,6-Sihydro4H-1,3-
oxazine), 2,2'-hexamethylene bis(5
, 6-jishi draw 4] (-1,3-oxazine),
2,2°-octamethylenebis(5,6-sihydro4
H-1,3-oxazine), 2,2'-1,4-cyclohexylenebis(5,6-cyhydro4H-1,3
-oxazine), 2,2'-bis(4-methyl-5
,6-sihydro4H-1,3-oxazine),
2.2'-bis(5-methyl-5,6-sihydro48
-1,3-oxazine), 2,2'-bis(6-methyl-5,6-sihydro-4H-1,3-oxazine)
, 2.2'-m-phenylenebis(5,6-dihydro-4H-1,3-oxazine), 2.2'-P-phenylenebis(5,6-dihydro-4H-1,3-oxazine) , 2,2'-m-phnylenebis(4-methyl-5
, 6-sihydro48-1,3-oxazine), 2.2
'-m-phenylenebis(5-methyl-5,6-dihydro4H-1,3-oxazine), 2,2'-m-phenylenebis(6-methyl-5,6-dihydro4H-1
, 3-oxazine), 2.2”-p-phenylenebis(
4-methyl-5,6-sihydro-48-1,3-oxazine).

2.2"-p-phenylenebis(5-methyl-5,6-
Shihydro 4H-1,3-oxazine), 2,2°
-p-phenylenebis(6-methyl-5,6-cyhydro-48-1,3-oxazine) and the like can be exemplified. Among these, 2,2°-bis(5,6-dihydro-48-1,3-oxazine), 2,2'-tetramethylenebis(5,6-dihydro-4H-1,3-oxazine), 2,2°-m-phenylenebis(5,6
-Sihydro4H-1,3-oxazine), 2,2
°-p-phnylenebis(5,6-sihydro4H-1,
3-oxazine) is preferred, and these can be used alone or as a mixture of two or more.

- In the present invention, a part of the polyoxazine derivative is an oxazoline derivative represented by the following formula (II) and/or a part of the polyoxazine derivative represented by the following formula (I).
I[) Ra -C-Rb )N \ / Rd -C-Re \,.

1 and Rf are the same as in formula (I). ) can be substituted with a monooxazine compound represented by Among the oxazoline derivatives, the amount of the polyoxazoline derivative used is preferably an amount that substitutes, for example, 90 mol% or less of the polyoxazine derivative, and more preferably 70 mol% or less of the polyoxazine derivative, and the amount of the monooxazoline derivative or monooxazine compound used is, for example, 30 mol% or less, and even 2
An amount that substitutes 5 mol% or less is preferred. When a polyoxazoline derivative and a monooxazoline derivative and/or a monooxazine compound are used together, it is preferable that the total amount thereof does not exceed 90 mol% of the polyoxazine derivative. R, Ra, Rb in formula (n)
, Rc and Rd and Ra in formula (III),
In the explanation of Rb, Rc, Rd, Re and Rf,
What has been explained in relation to formula (I) can be applied as is. In addition, m in formula (II) is an integer of 1 to 4, but 2 is particularly preferable among 2 to 4. When l is 2, R may be a direct bond, and R' in formula (III)
The monovalent aliphatic, alicyclic, or aromatic hydrocarbon group has the formula (n
) corresponds to R when n=1.

Specifically, the polyoxazoline derivatives include 2.2
°-bis(2-oxazoline), 2,2'-ethylenebis(2-oxazoline), 2,2'-tetramethylenebis(2-oxazoline), 2,2°-hexamethylenebis(2-oxazoline) , 2.2'-
Octadimethylenebis(2-oxazoline), 2,2°
-1,4-cyclohexylenebis(2-oxazoline)
, 2,2°-bis(4-methyl-2-oxazoline).

2.2′-bis(5-methyl-2-oxazoline).

2.2°-m-phenylenebis(2-oxazoline).

2.2”-p-phenylenebis(2-oxazoline).

2.2'-m-phenylenebis(4-methyl-2-oxazoline), 2,2°-m-phenylenebis(5-
Methyl-2-oxazoline), 2,2'-p-phenylenebis(4-methyl-2-oxazoline), 2゜2゜-
p-phenylenebis(5-methyl-2-oxazoline)
, 1,3.5-tris(2-oxazolinyl-2
) Benzene etc. can be exemplified. 2 of these
, 2°-bis(2-oxazoline), 2°2°-tetramethylenebis(2-oxazoline).

2.2°-m-phenylenebis(2-oxazoline).

2.2'-p-phenylenebis(2-oxazoline) is preferred.

Specifically, the monooxazoline derivatives include methyl-2-oxazoline, 2-ethyl-2-oxazoline,
2-propenyl-2-oxazoline.

2-phenyl-2-oxazoline, 2-tolyl-2-oxazoline, 2,5-dimethyl-2-oxazoline, 2
, 4-dimethyl-2-oxazoline, 2-phenyl-4
Examples include -methyl-2-oxazoline and 2-phenyl-5-methyl-2-oxazoline. Among these, 2-phenyl-2-oxazoline and 2-tolyl-2-oxazoline are preferred.

Specifically, the monooxazine compound includes 2-methyl-5,6-cyhydro-4H-1,3-oxazine, 2
-Ethyl 75,6-dihydro 4H-1,3-oxazine, 2-propenyl-5,6-dihydro 4H-1,3
-Oxazine, 2-phenyl-5,6-distal draw 4H
-1,3-oxazine, 2-tolyl-5,6-sihydro 4H-1,3-oxazine, 2-phenyl-4-methyl-5,6-sihydro 48-1,3-oxazine, 2
-phenyl-5-methyl-5,6-sihydro4H-1
,3-oxazine,2-phenyl-6-methyl-5,6
-Sihydro 4H-1,3-oxazine and the like can be exemplified. Among these, 2-phenyl-5,6-cyhydro-48-1,3-oxazine, 2-tolyl-5,6
- Dishidraw 4H-1,3-oxazine is preferred.

The ratio of thermoplastic resin (A) and polyoxazine derivative (B) used is A/B = 90/10 to 30/ by weight.
It is T.O. The proportion (weight ratio) of thermoplastic resin (A>) is 9
If it exceeds 0, the heat resistance and chemical resistance will not be sufficient, and if the proportion (weight ratio) of the polyoxazine derivative (B) exceeds 70, the mechanical properties will not be sufficient, so it is not preferable, but it is preferable to use the proportion (weight ratio). is A/B=80/20~40/
It is 60.

In the present invention, a composition consisting of a thermoplastic resin (A) and a polyoxazine derivative (B) is heated in the presence of a catalyst,
A polyoxazine derivative is polymerized in the thermoplastic resin matrix. Examples of such catalysts include protic acids, protic acid esters, Lewis acids, Lewis acid complexes, alkyl halides, and halogens. Examples of protonic acids include organic sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, benzenesulfone B, and p-toluenesulfonic acid; sulfuric acid, and phosphoric acid.

Examples include inorganic protonic acids such as sulfurous acid, phosphinic acid, phosphonic acid, perchloric acid, etc. Protonic acid esters include esters of the above protonic acids such as methyl, ethyl, and phenyl, such as methyl benzenesulfonate and benzene. Ethyl sulfonate, p-Methyl toluenesulfonate, p
- Organic sulfonic acid esters such as ethyl toluenesulfonate; inorganic protonic acid esters such as dimethyl sulfate, trimethyl phosphate, triphenyl phosphate, trimethyl phosphite, triphenyl phosphite, etc.;

Examples of Lewis acids and their complexes include titanium tetrachloride, tin tetrachloride, zinc chloride, aluminum chloride, trifluoroborane, and trifluoroborane ether complexes, and examples of alkyl halides include methyl iodide and ethyl iodide. .

Propyl iodide, butyl iodide, benzyl iodide.

Examples include benzyl bromide, and examples of the halogen include iodine. Among these, especially pKa is 23
Preferred are protic acids with a pKa of 5 or less, esters of protic acids with a pKa of 1.0 or less, Lewis acids, Lewis acid complexes, alkyl halides and iodine.

The amount of these catalysts to be used is not particularly limited, but 0.01 to 20 mol%, more preferably 0.05 to 15 mol%, particularly 0.1 to 10 mol%, based on the polyoxazine derivative (B). preferable.

In the present invention, the heating reaction temperature is preferably 160"C or higher, more preferably 170°C or higher, particularly 180°C or higher, and the reaction time may be any time that is sufficient to fully cure the target resin. In addition, this time varies depending on the type of raw materials used, usage ratio 1 reaction temperature, etc., but is preferably 10 seconds to 60 minutes, more preferably 20 seconds to 30 minutes,
The reaction, which is particularly preferably about 30 seconds to 15 minutes, can be carried out at normal pressure to increased pressure.

Although the heating reaction in the present invention can take various forms, the most preferred form is as follows.

The thermoplastic resin (A) and the polyoxazine derivative (B) are mixed uniformly under the melting conditions of the thermoplastic resin, and then the resulting composition is heated at a temperature higher than the flow start temperature, preferably at 200°C.
The catalyst is added and mixed at a temperature below C, more preferably below 180°C, particularly preferably below 160°C, and then the reactive composition (composition containing the catalyst) is filled into a mold of the desired shape. This is a method of heating to the above-mentioned reaction temperature and causing the reaction.

Many thermoplastic resins generally have a high flow initiation temperature, but by uniformly melting and mixing a polyoxazine derivative with the resin, the flow initiation temperature of the composition can be significantly lowered. Addition mixing is preferred.

In addition, the crosslinked resin of the present invention may contain reinforcing materials such as carbon fibers and glass fibers, various fillers, fillers, pigments, coloring agents, oxidation stabilizers, ultraviolet absorbers, mold release agents, etc., as necessary. Additives may be added as appropriate.

<Examples> Hereinafter, the present invention will be described in detail with reference to Examples, but the Examples are for illustrative purposes and the present invention is not limited thereto.

In the examples, "part" means "part by weight".

The glass transition point (Tg) was measured using a TMA (Thermomechanical Characteristics Measuring Apparatus) at a heating rate of 10° C./min. In addition, the flow start temperature is the temperature ('C) at which the polymer can be melt-extruded under a pressure of 100 kf/- using a flow tester equipped with a nozzle with a diameter of 0.5+w+ and a length of 1 m+n.
says.

Examples 1 to 3 and Comparative Example 1 Polycarbonate (intrinsic viscosity 0.81) (A) obtained by reacting bisphenol A and diphenyl carbonate by a transesterification method and 2,2°-m-phenylene bis(5 , 6-sihydro48-1.3-oxazine) (B) in the ratio (weight ratio) shown in Table 1,
It was melt-extruded at 250° C. using a 30 amφ twin-screw router. The flow onset temperatures of the resulting compositions are shown in Table 1.

Next, 100 parts of the pulverized product of the composition was thoroughly mixed with a predetermined amount of the catalyst shown in Table 1 using an S-type blender, and the resulting mixture was heated to a cylinder temperature of 140°C.

Injection molding was performed at a mold temperature of 200°C. that time,
The mold holding time was 5 minutes.

For comparison, injection molding was performed using the above polycarbonate alone under conditions of a cylinder temperature of 280°C and a mold temperature of 130°C.

The physical properties of the obtained molded products are shown in Table 1. Examples 1 to 3 are crosslinked resin molded products, and compared to Comparative Example 1, they have better heat resistance (rg) and il chemical resistance. It turns out that it is excellent.

Table 1 Examples 4 and 5 and Comparative Example 2
100 parts of H-1,3-oxazine) and polysulfone (manufactured by Union Carbide Co., Ltd.) in the amount shown in Table 2.

udel P-3500) and melt-extruded at 270°C using a 30m+φ two-wheeled router. The flow onset temperatures of the resulting compositions are shown in Table 2.

Next, 100 parts of the pulverized product of the composition was thoroughly mixed with a predetermined amount of the catalyst shown in Table 2 using an S-type blender, and the resulting mixture was charged into a mold heated to 235°C and held for 15 minutes. , reaction molded. Table 2 shows the physical properties of the obtained crosslinked resin molded product.

For comparison, heat resistance (Tg) and chemical resistance were measured using the polysulfone molded article, and the results are shown in Table 2.

'Example 6 318 parts of diphenyl terephthalate, 318 parts of diphenyl isophthalate and 479 parts of bisphenol A were melt-polymerized by a conventional method in the presence of 1 g of acetic acid and 0.1 parts to give a polyarylate (Tg: 169°C) with an intrinsic viscosity of 0.66. Obtained.

Next, 100 parts of the polyarylate and 100 parts of 2,2°-p-phenylenebis(5,6-sihydro-48-1,3-oxazine) were mixed, and 270 parts of the polyarylate was mixed using a two-screw Rougoux.
Melt mixed at °C. The flow onset temperature of the resulting composition was 85°C.

Next, 4 parts of ethyl benzenesulfonate was added to 100 parts of the composition.
The mixture was mixed uniformly, placed in a mold heated to 200°C, and held for 10 minutes. The Tg of the obtained crosslinked resin molded article was 270°C.

Claims (1)

[Claims] Thermoplastic resin (A) and the following formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) [In the formula, n represents an integer from 2 to 4, and R represents an n-valent aliphatic,
Represents an alicyclic or aromatic hydrocarbon group. However, when n=2, R may be a direct bond. Ra, Rb, Rc, Rd, Re
and Rf respectively represent a hydrogen atom, an aliphatic hydrocarbon group having 3 or less carbon atoms, and an aromatic hydrocarbon group having 7 or less carbon atoms,
These may be the same or different. ] In the presence of a catalyst, a composition consisting of a polyoxazine derivative (B) and having a weight ratio of thermoplastic resin (A) to polyoxazine derivative (B) of 90:10 to 30:70 is prepared. A method for producing a cross-linked resin, characterized by subjecting it to a heating reaction.