JPH1036480A - Method for producing isocyanate group-containing polyolefin-based modifier - Google Patents

Abstract

(57) [Problem] To provide a method for producing an isocyanate group-containing polyolefin-based modifier. SOLUTION: A specific hydroxyl group-containing poly (ethylene-butylene) copolymer is reacted with an organic diisocyanate at a ratio at which isocyanate groups are larger than hydroxyl groups.
This is a method for producing an isocyanate group-containing polyolefin-based modifier having a free isocyanate content of less than 1% by weight by removing unreacted organic diisocyanate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an isocyanate group-containing polyolefin-based modifier capable of modifying various resins.

[0002]

2. Description of the Related Art Epoxy resins, acrylic resins, melamine resins, polyamide resins, polyester resins, urea resins, phenol resins, polyurethane resins, etc. are used as resins used for adhesives, coating agents, paints, structural materials and the like. . Among them, the hard type resins have advantages such as high hardness and high durability, but have problems such as poor flexibility and toughness (for example, when used as an adhesive, the adhesive strength is high, but with a slight shock, Problem of peeling). In order to improve such problems, improvement with a modifier has been widely attempted.

For example, conventional epoxy resin modifiers include terminal carboxylated poly (butadiene-acrylonitrile) (abbreviated as CTBN) and polypropylene glycol diglycidyl ether (abbreviated as DGEPPG).
Etc. However, although the CTBN modification enables toughening of the resin, it causes a problem that the weather resistance is reduced due to the double bond contained in the CTBN. Also, D
Modification by GEPPG has problems such as lowering the glass transition point and strength.

In recent years, in the field of adhesives, coatings and paints, polyolefin-based materials such as polypropylene and polyethylene have been increasingly used instead of polyvinyl chloride-based materials due to environmental problems. . However, in conventional resins, those having good adhesion and adhesion to polyolefin have insufficient durability, and those having good durability have insufficient adhesion and adhesion. .

US Pat. No. 5,378,761 discloses a reaction product of hydrogenated polybutadiene and diphenylmethane diisocyanate (abbreviated as MDI) and a reaction product of hydrogenated polybutadiene and isophorone diisocyanate (abbreviated as IPDI) of epoxy resin. An example used for reforming is disclosed. Also, US Pat. No. 5,459,200 discloses hydrogenated polybutadiene and polyisocyanate, IPDI, or hexamethylene diisocyanate (abbreviated as HDI).
An example is disclosed in which a reaction product of the above is used for modifying an epoxy resin.

However, the above-mentioned specification does not consider the content of so-called free isocyanate which was present in the obtained modifier and did not participate in the reaction. In particular, the reaction product described in U.S. Pat. No. 5,378,761 has a high free isocyanate content of 3.4 to 4.1% by weight. When the content of the free isocyanate is large as described above, there is a problem in terms of odor, and the free isocyanate reacts with additives such as a curing agent to reduce various physical properties.

[0007]

SUMMARY OF THE INVENTION The present invention has been intensively studied and studied in order to improve the conventional problems. As a result, the isocyanate group-containing polyolefin-based modifier obtained by the production method of the present invention is effective. And reached the present invention.

[0008]

That is, the present invention is as follows. (A) A random copolymer or a block copolymer represented by the following general formula (1), wherein the molar ratio of ethylene / butylene (m / n in the formula (1)) is 90/10 to 10/90.
Content of free isocyanate obtained by reacting a poly (ethylene-butylene) copolymer having hydroxyl groups at both ends with an organic diisocyanate under conditions of excess isocyanate groups, and then removing unreacted isocyanate monomers. Is less than 1% by weight.

[0009]

Embedded image

(B) In the following general formula (2), a random copolymer or a block copolymer,
The butylene molar ratio (m / n in formula (2)) is 90/10
10/90, X = OH, X '= H or X = H,
A poly (ethylene-butylene) copolymer having a hydroxyl group at one end where X '= OH is reacted with an organic diisocyanate under conditions of an excess of isocyanate groups, and then free radicals obtained by removing unreacted isocyanate monomers. A process for producing an isocyanate group-containing polyolefin-based modifier having an isocyanate content of less than 1% by weight.

[0011]

Embedded image

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The hydroxyl group-containing poly (ethylene-butylene) copolymer used in the present invention has the formula (1)
And (2), a poly (ethylene-copolymer) which is a random or block copolymer obtained by living polymerization such as radical polymerization or anionic polymerization of ethylene and butylene.
It can be obtained by grafting a vinyl alcohol compound to a (butylene) copolymer or treating a terminal polymerization initiator component.

The molar ratio of ethylene to butylene (m / n in the formulas (1) and (2)) of the hydroxyl group-containing poly (ethylene-butylene) copolymer is 90/10 to 10/90. When the amount of ethylene exceeds 90 mol% or less than 10 mol%, the crystallinity of the copolymer increases and the melting point increases, so that it is difficult to obtain the desired modifier.

The number average molecular weight of the hydroxyl group-containing poly (ethylene-butylene) copolymer in the formulas (1) and (2) is
500 to 10,000, and a preferred number average molecular weight is 1,000 to 9,000.

If the hydroxyl group-containing poly (ethylene-butylene) copolymer has a number average molecular weight of less than 500, it is merely an aliphatic alcohol compound, and the reaction product with the organic diisocyanate has high crystallinity and a high melting point. Therefore, it is difficult to obtain the desired modifier. When the number average molecular weight exceeds 10,000, the hydroxyl group-containing poly (ethylene-
The (butylene) copolymer originally has low compatibility with other resins and isocyanates, and the viscosity of the hydroxyl group-containing poly (ethylene-butylene) copolymer becomes high. Become smaller.

The average hydroxyl group content of the poly (ethylene-butylene) copolymer having hydroxyl groups at both ends in the formula (1) is 1.5 to 2.5 per molecule, particularly 1.8.
~ 2.0 are preferred. If the number of hydroxyl groups is less than 1.5, the poly (ethylene-butylene) copolymer containing hydroxyl groups at both ends will be lost. When the number of hydroxyl groups exceeds 2.5, the viscosity of the obtained isocyanate group-containing polyolefin modifier increases, and the workability deteriorates.

Further, the average hydroxyl group content of the poly (ethylene-butylene) copolymer having a hydroxyl group at one terminal in the formula (2) is 0.5 to 1.5 per molecule, and particularly preferably 0.5 to 1.5 per molecule.
8 to 1.0 are preferred. When the number of hydroxyl groups is less than 0.5, a simple blend of an organic diisocyanate and a poly (ethylene-butylene) copolymer results. Therefore, hydroxyl-containing poly (ethylene-butylene)
Since the compatibility between the copolymer and the organic diisocyanate is low, they are separated and the stability over time becomes poor. When the number of hydroxyl groups exceeds 1.5, the poly (ethylene-butylene) copolymer having one terminal hydroxyl group is not obtained.

Specific examples of the hydroxyl group-containing poly (ethylene-butylene) copolymer include, for example, HPM-1202 and HPVM-2202 of the Clayton Liquid Series manufactured by US Shell as random polymer types.

The organic diisocyanate used in the present invention includes HDI, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, and 2,2,4-trimethylhexaheth. Len-1,6-diisocyanate,
Aliphatic diisocyanate such as 2,4,4-trimethylhexahylene-1,6-diisocyanate, IPDI,
2,4-cyclohexyl diisocyanate, 4,4'-
Alicyclic diisocyanates such as dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated trimethyl xylylene diisocyanate, and 4,4'-
MDI, 2,4'-MDI, 2,2'-MDI, 4,
4'-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, paraphenylene diisocyanate, 2,4-tolylene diisocyanate (2,4-TD
I), non-yellowing diisocyanates such as aromatic diisocyanates such as 2,6-TDI, ortho-xylylene diisocyanate, meta-xylylene diisocyanate, para-xylylene diisocyanate, and tetramethyl xylylene diisocyanate, and mixtures thereof. And preferred organic diisocyanates are HDI, IPDI, TDI, and MDI, which are economically advantageous.

Further, when the step of removing free isocyanate is by distillation, HDI or TDI having a high vapor pressure is preferable among the above-mentioned organic diisocyanates.

The reaction catalyst for synthesizing the isocyanate group-containing polyolefin-based modifier in the present invention includes:
Known so-called urethanization catalysts such as organic metal compounds such as dioctyltin dilaurate, organic amines such as triethylenediamine, and salts thereof can be used.

In the present invention, the isocyanate group / poly (ethylene butylene) -containing poly (ethylene butylene) is used to produce an isocyanate group-containing polyolefin-based modifier.
The molar ratio of the hydroxyl group is a ratio exceeding 1, specifically, 1
0 to 100 is preferable, and 20 to 80 is most preferable.

In the present invention, the isocyanate group / poly (ethylene butylene) -containing poly (ethylene butylene) -containing one-terminal hydroxyl group is used to produce the isocyanate group-containing polyolefin modifier.
The molar ratio of hydroxyl groups is 2 or more, and specifically 10 to 10
0 is preferable, and 20 to 80 is most preferable.

The reaction temperature is 15 to 100 ° C, preferably 40 to 90 ° C. If the temperature is lower than 15 ° C., since the isocyanate group and the hydroxyl group hardly react with each other, a simple blend of an organic diisocyanate and a poly (ethylene-butylene) copolymer results. For this reason, since the compatibility between the hydroxyl group-containing poly (ethylene-butylene) copolymer and the organic diisocyanate is low, they are separated and the stability over time is poor. When the temperature exceeds 100 ° C., not only urethane groups but also allophanate groups are generated by the reaction of urethane groups and isocyanate groups, or isocyanate groups such as uretdione groups and isocyanurate groups react with each other, and the desired modifier is used. Is difficult to obtain.

The reaction method for synthesizing the isocyanate group-containing polyolefin-based modifier in the present invention can be produced by a solid reaction method or a solvent reaction method. In the production method of the present invention, the isocyanate group-containing polyolefin-based modifier is obtained through the step of removing free isocyanate. Therefore, a solid reaction in which the loss is small and the removal step is easy is preferable.

After the reaction, the unreacted isocyanate is removed so that the free isocyanate is less than 1% by weight. As the removal method, distillation method under reduced pressure, once dissolved in a good solvent,
Next, there are a reprecipitation method in which it is poured into a poor solvent, an extraction method in which it is dispersed in a poor solvent, and then it is poured into a good solvent.
The removed isocyanate monomer can be recovered and reused.

The free isocyanate content contained in the isocyanate group-containing polyolefin-based modifier thus obtained is less than 1% by weight, preferably less than 0.5% by weight.

When the content of free isocyanate is 1% or more, odor due to vapor of organic isocyanate,
There is a health problem for the handling worker. In addition, free isocyanate reacts with additives such as a curing agent to adversely affect various physical properties.

Examples of applications of the obtained isocyanate group-containing polyolefin-based modifier include: improving the adhesion to polyolefin by adding to an adhesive; improving the adhesion to polyolefin by adding to paint; Can be achieved. In addition, it is used for applications such as vinyl chloride resin, polyolefin resin, epoxy resin, and acrylic resin for structural materials for softening and toughening the resin.

When using the isocyanate group-containing polyolefin-based modifier obtained by the present invention, the resin to be modified and the modifier obtained by the present invention are mixed and stirred at an appropriate ratio, and if necessary, stirred. Upon heating, the modifier reacts with the resin to be modified. Thereafter, if necessary, a pigment, a dye, an antioxidant, an ultraviolet absorber, a viscosity stabilizer, a solvent, and the like are blended, and the composition can be used in a form suitable for each use such as a paint, an adhesive, a coating agent, and the like. .

[0031]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. In Examples and Comparative Examples, “parts” and “%” are “parts by weight” and “% by weight”. The isocyanate content was JIS K-6806, and the viscosity was JIS K-683.
3. Free isocyanate was measured by gel permeation chromatography.

Example 1 A four-necked flask equipped with a stirrer, a thermometer, a cooling tube and a nitrogen gas inlet tube was charged with a poly (ethylene-butylene) copolymer having a number average molecular weight of 3,600 and having both terminal hydroxyl groups (commercially available) Name: H
32.4 parts of PVM-2202, manufactured by Shell), 6
Warmed to 0 ° C. To this, 67.6 parts of 4,4'-MDI was charged, and a urethanization reaction was carried out at 80 ° C for 4 hours. The obtained reaction product is designated as RM-1. RM-1 had an isocyanate content of 21.9% and free MDI of 65.3%. Next, RM-1 was extracted with normal-hexane,
An isocyanate group-containing polyolefin compound MA-1 was obtained. MA-1 has an isocyanate content of 1.83%,
The viscosity is 39,000 cP / 25 ° C.
3%.

Example 2 In the same reactor as in Example 1, 4 HPVM-2202 was added.
4.8 parts were charged and heated to 60 ° C. Then, 55.2 parts of IPDI and then 0.02 part of DBTDL were charged and reacted at 80 ° C. for 4 hours. The resulting reactant is
M-2. The isocyanate content of RM-2 is 1
9.9% and free IPDI was 52.5%. Next, RM-4 was subjected to normal-hexane extraction to obtain an isocyanate group-containing polyolefin compound MA-2. M
A-2 has an isocyanate content of 2.05% and a viscosity of 3
4,000 cP / 25 ° C., free IPDI was 0.1%.

Example 3 A reaction apparatus similar to that of Example 1 was charged with a number average molecular weight of 4,000.
43. A poly (ethylene-butylene) copolymer having one terminal hydroxyl group (trade name: HPVM-1202, manufactured by Shell).
Four parts were charged and heated to 60 ° C. This is 2,4-TDI
56.6 parts of dibutyltin dilaurate (DBTDL)
0.02 parts), and urethanization reaction was carried out at 80 ° C. for 4 hours. The obtained reaction product is designated as RM-3.
RM-3 had an isocyanate content of 26.9% and free TDI of 54.7%. Next, RM-1 is set to 170
Free T by thin film distillation under the condition of
The DI was removed to obtain an isocyanate group-containing polyolefin modifier MA-3. MA-3 had an isocyanate content of 1.08%, a viscosity of 37,000 cP / 25 ° C, and a free TDI of 0.2%.

Example 4 In the same reactor as in Example 1, 4 HPVM-1202 was added.
8.8 parts were charged and heated to 60 ° C. HDI to this 5
1.2 parts and 0.02 part of DBTDL were charged and reacted at 80 ° C. for 4 hours. The obtained reaction product is designated as RM-4.
RM-4 had an isocyanate content of 25.1% and free HDI of 49.2%. Next, RM-4 is set to 150
Free H by the thin film distillation under the condition of 0.5 ° C. × 0.5 torr.
The DI was removed to obtain an isocyanate group-containing polyolefin modifier MA-4. MA-4 had an isocyanate content of 1.02%, a viscosity of 35,000 cP / 25 ° C, and a free HDI of 0.1%.

Comparative Examples 1 to 4 RM-1 to RM-4 were designated as Comparative Examples 1 to 4. Examples 1 to 4 and Comparative Examples 1 to 4 are collectively shown in Tables 1 and 2.

[0037]

[Table 1]

[0038]

[Table 2]

Application Examples 1 to 4 and Application Comparative Examples 1 to 4 [Adhesion Test] 5 parts of MA-1 was added to 100 parts of Epicoat 1009 (made of Yuka Shell Epoxy), and
Heated at ° C for 1 hour. After blending 5 parts of diethylaminopropylamine as a curing agent, the composition was applied to a polypropylene plate so as to have a thickness of 50 micrometers,
After curing at room temperature for 7 days, Application Example 1 was obtained. Further, in the same manner as in the application example 1, MA-2 was used instead of MA-1.
Application Examples 2 to 4 and Application Comparative Examples 1 to 4 were obtained using RM-1 to RM-4. Application Examples 1-4, Application Comparative Examples 1
For No. 4, the adhesion of the coating film was evaluated by the grid test method of JIS K-5400. The remaining amount of the coating film is 100% to 70%
Was evaluated as ○, 70% to 30% as Δ, and less than 30% as X. Table 3 shows the formulation examples and the results of the adhesion test.

[0040]

[Table 3]

Application Examples 5 to 8 and Application Comparative Examples 5 to 8 [Fracture toughness test] Five parts of MA-1 were added to 100 parts of Epicoat 1009 (manufactured by Yuka Shell Epoxy), and the mixture was heated at 80 ° C. Heated for 1 hour. To this, 15 parts of 4,4'-diaminodiphenyl sulfone was added and mixed at 120 ° C until uniform. The mixture was poured into a mold having a width of 100 mm, a height of 20 mm and a depth of 10 mm.
The composition was cured at × 2 hours + 180 ° C. × 4 hours to obtain Application Example 5. Also, in the same manner as in the application example 5, MA-1
Was used in place of MA-2 to 4 and RM-1 to 4 to obtain Application Examples 6 to 8 and Application Comparative Examples 5 to 8. Application Example 5
8, a 5 mm incision is made in the center of the applied comparative examples 5 to 8, and a 5 mm crack is formed with a sharp knife,
The test piece was used for measuring the fracture toughness value (K _1C ). K _{1C of} this test piece was measured by ASTM E-399. Table 4 shows the formulation examples and the results of the fracture toughness measurement test.

[0042]

[Table 4]

[0043]

As described above, by using the isocyanate group-containing polyolefin-based modifier obtained according to the present invention, it is possible to improve the adhesion of paints and adhesives to polyolefins, and to improve the vinyl chloride resin, polyolefin resin, and epoxy resin. , An acrylic resin or the like, and toughness.

[Brief description of the drawings]

FIG. 1 is a front view of the shape of a test piece used for a fracture toughness measurement test.

Claims (2)

[Claims] 1. A random copolymer or a block copolymer represented by the following general formula (1), wherein a molar ratio of ethylene / butylene (m / n in the formula (1)) is 90/10 to 1
A free isocyanate obtained by reacting a poly (ethylene-butylene) copolymer having 0/90 hydroxyl groups at both ends with an organic diisocyanate under an isocyanate group excess condition, and then removing an unreacted isocyanate monomer. Of isocyanate group-containing polyolefin-based modifier having a content of less than 1% by weight. Embedded image 2. In the following general formula (2), it is a random copolymer or a block copolymer, and the ethylene / butylene molar ratio (m / n in the formula (2)) is 90/10 to 10.
/ 90, X = OH, X '= H or X = H, X' =
Free isocyanate content obtained by reacting an organic diisocyanate with a poly (ethylene-butylene) copolymer having a hydroxyl group at one end, which is OH, and an organic diisocyanate, and then removing an unreacted isocyanate monomer. A process for producing an isocyanate group-containing polyolefin-based modifier having an amount of less than 1% by weight. Embedded image