JP3442091B2 - Reactive organopolysiloxane-polylactone copolymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a novel reactive silicone.
For more details, please refer to the new block copolymers
Responsive organopolysiloxane-polylactone copolymer
Related. [0002] 2. Description of the Related Art Organopolysiloxanes are resistant to heat and heat.
Excellent cold resistance, weather resistance, chemical resistance, flame retardancy, electrical properties, repellency
Shows unique interface properties such as water-based, defoaming properties, and mold release properties
Therefore, it is widely used in industry. These excellent properties
Organopolicy to add to existing organic polymer compounds
Loxane can be directly blended with organic polymer compounds or copolymerized.
Many attempts have been made to do so. However, in general
The organopolysiloxane is compatible with organic polymer compounds.
Molded product when solubility is poor and the former is a liquid compound
Oozes out on the surface and dissipates from the surface by contact etc.
Keeping the surface properties of molded products constant over a long period of time
Have difficulty. Solid organopolysiloxane compounds, examples
For example, organic polymers as well as cross-linked silicone rubber
It is difficult to mix uniformly with the compound. Therefore,
To improve compatibility, interfacial properties and reactivity,
Lisiloxane can be converted to alkyl, aralkyl, polyether
Group, amino group, carboxyl group, epoxy group, etc.
In many cases, those modified with an organic base are used. But
Heat resistance, cold resistance, weather resistance
There is a problem that the properties and the hydrolysis resistance are reduced and the coloring is caused.
Also, the compatibility with the organic polymer compound is insufficient,
Decomposition during molding due to poor heat resistance of organic groups
Or loosen from the molded product or cause molding failure
Limited use and target organic polymer compounds
Was. Copolymerization of organopolysiloxane and polyester
The body is Japanese Patent Publication No. 48-4117, Japanese Patent Publication No. 50-3964.
8, and Japanese Patent Publication No. 1-49797.
Apply interface properties to organic polymer compounds
But with the introduction of more reactive functional groups
There is no. [0003] SUMMARY OF THE INVENTION The present invention provides a novel reaction
More information on functional silicone block copolymers
Is an organopolysiloxane-polylactone copolymer.
Novel reactive olefins obtained by introducing reactive groups
Provide a ganopolysiloxane-polylactone copolymer
It is in. [0004] SUMMARY OF THE INVENTION The present invention relates to a single molecule.
Has at least one hydrogen atom directly connected to an iodine atom
Organopolysiloxane and alkenyl group in one molecule
A polylactone oligomer having at least one or more
A reactive functional group was introduced into the reactantGeneral below
Formula (1) or (2)Reactive organopolysilo
It relates to a xan-polylactone copolymer.Embedded image Embedded image (Where a, b and c are positive numbers, d is a positive number of 2 to 20, A
Is a functional group excluding an unsaturated group. )1 minute in the present invention
At least one hydrogen atom directly connected to a silicon atom
The molecular structure of the organopolysiloxane having the above
May contain structures, networks, or three-dimensional structures
Of these homopolymers or a mixture of two or more
Compounds can also be used. [0005] The reactive organopolysiloxane of the present invention
Polylactone copolymer is obtained by the following method, especially
However, it is not limited to these. 1. (A) A hydrogen atom directly connected to a silicon atom in one molecule
An organopolysiloxane having at least one of
(B) at least one alkenyl group in one molecule
A polylactone oligomer having the compound of (a)
With respect to the compound of (b), the hydrogen atom of the compound of (a)
The total number of moles is the total number of moles of the alkenyl group of the compound of (b).
Reaction in excess to the non-hydrolyzed form
Of organopolysiloxane-polylactone copolymer
(C) a reactive functional group,
For example, epoxy group, amino group, hydroxyl group, carboxyl
Group, acyl group, mercapto group, isocyanate group, urea
Id group, amide group, imide group, imino group, aldehyde
Group, nitro group, nitrile group, oxime group, azo group, hydride
Select from razone, alkoxy, alkoxysilyl, etc.
Ethylenically unsaturated group-containing monomer having any selected group
Obtained by reacting the body. Further, the compound of (a)
With respect to the compound of (c), the hydrogen atom of the compound of (a)
The total number of moles is based on the total number of moles of unsaturated groups in the compound (c)
And then reacting it in excess to obtain the copolymer.
And the compound of (b). (A)
Simultaneously reacting the compound with the compound of (b) and the compound of (c)
You may let it. Further, the compound of (a) is
After reacting with the compound or the compound of (c), in one molecule
And at least one hydrogen atom directly connected to the silicon atom
Of organopolysiloxane oligomer and acid present on it
And then reacting the compound of (c) or the compound of (b)
It is also obtained by reacting with a compound. [0006] 2. (A) Directly connected to silicon atom in one molecule
Organopoly with at least one hydrogen atom
Low alkenyl groups in one molecule of siloxane and (b)
React with a polylactone oligomer having at least one
Non-hydrolyzable organopolysiloxane-polylac
Ton copolymer, having reactivity with the copolymer
Functional groups such as epoxy groups, amino groups, hydroxyl groups,
Ruboxyl group, acyl group, mercapto group, isocyanate
Groups, ureido groups, amide groups, imide groups, imino groups,
Aldehyde group, nitro group, nitrile group, oxime group, azo
Group, hydrazone group, alkoxy group, alkoxysilyl group
Having at least one arbitrary group selected from the group consisting of
Lisiloxane or silane in the presence of acid or alkali
It is obtained by reacting below. And reacting with the compound of (a).
Organopolysiloxy having at least one functional group having hydrophilicity
Reaction of sun or silane in the presence of acid or alkali
After the reaction, the compound may be reacted with the compound (b). Reactive organopolysiloxane-polylac
Specific examples of the ton copolymer include the following:
However, the present invention is not limited to these.Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image [0008] In the present invention, the reactive organopolysiloxy
Sun-polylactone copolymers are known per se from the prior art.
Can be produced by a combination of the above synthesis methods. An example
For example, the above equation(3)In the case of a compound represented by
Methyl hydrogen polysiloxaneEmbedded image andEmbedded image Obtained by an addition reaction in the presence of a platinum-based catalyst.
It is. Similarly, the above equation(5)Of the compound represented by
If the corresponding methyl hydrogen polysiloxaneEmbedded image andEmbedded image Obtained by an addition reaction in the presence of a platinum-based catalyst.
It is. Further, the above equation(7)Field of the compound represented by
If the corresponding methyl hydrogen polysiloxaneEmbedded image A platinum-based catalyst
By the addition reaction in the presence ofEmbedded image The compound of the formulaEmbedded image The amino-modified polysiloxane represented by
It is obtained by doing. Further, the above equation(8)Of the compound represented by
The corresponding methyl hydrogen polysiloxane
Vinyltrimethoxysilane (C
H₂= CHSi (OCH₃)₃) In the presence of a platinum-based catalyst
To give an addition reaction. Of course,
As for the manufacturing method, it is particularly limited to those described above.
There is no. In the present invention, the reactive organopolysiloxy is used.
The sun-polylactone copolymer is, for example, paper / pulp.
It can be used as a modifier, fiber surface modifier, etc.
Diapers, napkins, toilet paper,
Durability and weather resistance for paper and pulp products such as shpaper
Gives a soft, soft texture and hydrophilicity to the fiber surface
As a modifier, wool, silk, hemp, cotton,
Natural fiber such as asbestos, rayon, cupra, a
Recycled fibers such as acetate, polyester, polyester
Polyester, polyacrylonitrile, vinylon, polyvinyl chloride
Nilidene, polyvinyl chloride, polyethylene, polypropylene
Such as organic synthetic fiber, glass fiber, carbon fiber, etc.
Any fiber of inorganic synthetic fibers may be used.
Any form of material, knit, non-woven fabric, resin processed cloth, etc.
Even the surface of the fiber can be treated,
The fabric has a durable and weather-resistant soft texture and parent
Water-based. For this reason, industrial and household softeners and
It can be incorporated into industrial and household detergents. Further, for skin, hair, bath, etc.
It can be used for cosmetics and toiletries, such as skin and hair.
Give your hair a moist, moist and smooth feel
Make it possible. Further, natural rubber and styrene-butadiene
Polymerized rubber, butadiene rubber, isobutylene-isoprene
Copolymer rubber, chloroprene rubber, acrylonitrile lube
Tadiene copolymer rubber, isoprene rubber, ethylene-pro
Pyrene-diene copolymer rubber, ethylene-propylene copolymer
Synthetic rubber such as synthetic rubber, acrylonitrile-butadiene
-Styrene copolymer, polystyrene, polyurethane, d
Synthetic resin such as epoxy or inorganic filler or glass
Can be used for machine materials, heat resistance, cold resistance, weather resistance
Properties, chemical resistance, flame retardancy, water repellency, release properties, hydrolysis resistance
Properties, oil resistance, slip resistance, anti-blocking properties, wear resistance,
Provides low compression distortion, antistatic properties, antifogging properties and stress relaxation
I do. In particular, when used with epoxy resin, etc.
If the composition is a semiconductor encapsulant, an electrical laminate,
Used for electronic components such as sensors, resistors, potentiometers, and transformers
can do. Further, polyester resin is used as a paint modifier.
Can be blended with paint resin consisting of
Resistance to metal, wood, concrete, etc.
Enables painting with excellent antistatic properties. Accordingly, the present invention relates to a reactive organopolysilo.
Xan-polylactone copolymer
Reactive Organopolysiloxane-Polylactone Copolymerization
Body is paper / pulp modifier, fiber surface modifier, cosmetics
・ Toiletries additive, rubber / resin modifier, paint
It is suitably used as a modifier. [0017] Now, the present invention will be described in further detail with reference to Examples.
Although described, the present invention is limited to these examples.
However, what embodies the technical idea of the present invention is
Included within the scope. [0018]Example 1 Equipped with mechanical stirrer, condenser, thermometer and nitrogen inlet
Methyl hydride in a 1,000 ml three-necked flask
Rogenpolysiloxane Embedded image 150g, toluene 200g, 20ppm as platinum
Thus, a 10% methanol solution of chloroplatinic acid was added.
The mixture is maintained at a temperature of 80-100 ° C.
Allyl terminated polycaprolactone at a rate Embedded image 217 g and allyl glycidyl ether 27 g were gradually added.
Added. The end of this reaction is determined by the AgNO3 test for SiH.
The test was judged to be negative. The reaction mixture is then
Neutralize with HCO3, filter and 50 rot
After removing the solvent at 1 ° C./1 mmHg,
As a result, 353 g of a copolymer having a molecular weight of 5,300 was obtained. Embedded image [0019]Reference Example 1 Dihydropolydimethylsiloxane Embedded image 100 g, allyl-terminated polycaprolactone Embedded image 138 g, toluene 200 g, and platinum 20 ppm
The same operation as in Example 1 was performed using the following formula.
After obtaining 415 g of a copolymer having a molecular weight of 2,700,
200 g of toluene, the following formula Embedded image 10.6 g of cyclic hydromethylpolysiloxane, sulfuric acid 5
0 ppm was added. The mixture is left to react for 4 hours at room temperature.
After neutralization with NaHCO3, 20p
pm in a 10% methanol solution of chloroplatinic acid
Was. Maintain the temperature at 80-100 ° C. in this mixture
Allyl methacrylate at similar speed Embedded image 27 g were added slowly. The end of this reaction is
The AgNO3 test performed was judged to be negative. Then
The reaction mixture was neutralized with NaHCO3, filtered, and rotary evaporated.
After removing the solvent at 50 ° C./1 mmHg by a generator,
235 g of a copolymer having a molecular weight of 4,200 represented by the following formula:
353 g of a polymer was obtained. Embedded image Reference example2 All-terminal allylated polycaprolactone Embedded image 248 g, dihydropolydimethylsiloxane Embedded image 252g, toluene 200g and platinum 20ppm
The same operation as in Comparative Example 1 was performed, and represented by the following formula.
430 g of a copolymer having a molecular weight of 6,900 was obtained. Embedded image Next, in the same apparatus, the total amount of this copolymer (430 g),
200 g of toluene, the following formula Embedded imageCyclic amino-modified polysiloxane of 39.7 g, TMAH
(Tetramethylammonium hydroxide) 500
ppm. This mixture is brought to a temperature of 80-100 ° C.
After reacting for 7 hours while maintaining, 140-150 ° C / 1m
Decompose and remove TMAH with mHg and remove solvent
After that, 235 g of a molecular weight of 7,60 represented by the following formula:
Thus, 445 g of a copolymer was obtained. Embedded image Embodiment2, Reference example3-4, Comparative Example 1 Polyol (polycaprolactone diol, MW200
0), MDI, 1,4-butanediol are converted to NCO / O
H (equivalent ratio) is 1.05, 1,4-butanediol / Po
Liol (molar ratio) was mixed at a ratio of 2.0
100 parts by weight of the above example1And reference examples1-2Get in
Reactive organopolysiloxane-polylactone
Add 10 parts by weight of each polymer and mix at 80 ° C for 1 hour
Together, a prepolymer was obtained. Further, as Comparative Example 1,
A polymer-free product was also prepared. Cast these, 80
Curing for 1.5 hours at 120 ° C and 20 hours at 120 ° C
After aging for one week, the product should be in accordance with JIS K-7311.
The properties were measured. Oil resistance and heat resistance using the same sample
And water resistance were measured. [Table 1]Embodiment3, Reference example5-6, Comparative Example 2 Equipped with mechanical stirrer, condenser, thermometer and nitrogen inlet
Solvent toluene in a 2,000 ml three-necked flask
250 g, butyl acetate 250 g, radical catalyst Di
Put 5 g of -tert-butylperoxide,
Heat to 120 ° C under nitrogen gas atmosphere,
Mixed liquid (styrene 200g, methyl methacrylate 50
g, butyl acrylate 122 g, methacrylic acid 3 g,
125 g of hydroxyethyl acrylate) and radical
3 g of AIBN as an initiator is stirred at a constant speed from a dropping funnel.
It was dripped down in 4 hours. Further, the above embodiment1And reference examples
1-2The reactive organopolysiloxane-poly obtained in
10 g of each lactone copolymer was added, and the
2 g of AIBN, which is a medium, is added and stirred for 120 hours.
Aging reaction at ℃, transparent resin solution of 50% non-volatile content
I got Further, as Comparative Example 2, the copolymer was not added.
Also prepared. For these samples, non-yellowing polyiso
Cyanate is blended, cured coating film is adjusted, and physical properties are evaluated.
Was. [Table 2][0023] The present invention provides a novel reactive organopolicy.
It relates to a loxane-polylactone copolymer.
The reactive organopolysiloxane-polylactone copolymer
Coalescence includes paper / pulp modifiers, fiber surface modifiers, cosmetics
And toiletry product additives, rubber and resin modifiers, coatings
It is suitably used as a feed modifier.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08G 77/00-77/62

Claims (1)

(57) Claims 1. An organopolysiloxane having at least one hydrogen atom directly bonded to a silicon atom in one molecule, and a polyorganosiloxane having at least one alkenyl group in one molecule. It is represented by the following general formula (1) or (2) in which a reactive functional group is introduced into a reaction product with a lactone oligomer.
Polylactone copolymer - reactive organopolysiloxane. Embedded image Embedded image (Where a, b and c are positive numbers, d is a positive number of 2 to 20, A
Is a functional group excluding an unsaturated group. )