CN85102259A - The preparation of segmented copolymer - Google Patents

Abstract

The synthetic SDS of institute of the present invention is that initiator, hexanaphthene are that solvent makes with n-Butyl Lithium or s-butyl lithium.In order to reduce the set deformation volume of SDS, employing is added a small amount of conjugated diolefin in styrenic in the first step polymerization process, the conjugated diolefin consumption is that 0.01～5.0% (weight) (is benchmark with the total consumption of divinyl) optimum amount is 0.05～1.50%.The joining day of conjugated diene was advisable with the first step styrene polymerization in 0.2～15 minute, preferably was controlled at 0.5～6.0 minute.The set deformation volume of the SDS that is synthesized like this＜30%, and do not influence other physical and mechanical properties of product.

Description

The preparation of segmented copolymer

International Patent classificating number: C08F 236/00, C08F 297/04.

Reference:

US 3，281，383 1966 Zelinski

BP 1，271，045 1972 Kray

BP 1，300，326 1972

US 3，778，490 1973 Hsieh

US 3，939，224 1976 Horiie

“Synthesis of radial thermo-Plastic elastomers”，H.L.Hsieh，《Rubber Chemistry and Technology》，Vol 49，No，1305（1976）。“Synthesis and Properties of block Copolymers”，Le-Khac Bi and L.J.Fetters，《Macromolecules》，Vol.9，No.5，733-742（1976）。“Structure-Property relations in amorphous and Crystallizable ABA triolock Copolymers”，M.Morton，《Rubber Chemistry and Technology》，Vol.56，No.5，1096-1110（1983）。

Technical background:

This patent is about reducing segmented copolymer SDS(S: the D expression styrene monomer): the technology of set deformation volume expression conjugated diolefin monomer).Known employing lithium alkylide is that initiator can the synthesizing styrene class and many kinds of segmented copolymers of conjugated diolefin, as U.S.Pat No.3,281,383.U.S.Pat.No 3,778, and 490 have introduced the adiabatic polymerisation process of synthetic SDS.U.S.Pat.No.3939224 is in synthetic SBS resin polymerization process as sheet material or book film, the moderator of making styrene polymerization with few butadiene is added in the styrene monomer, and the few butadiene consumption is different because of reactor size and polymerizing condition.But, all do not relate to the excessive improvement problem of SBS set deformation volume in the above-mentioned patent.

The detailed description of this patent:

At present, preparation line style or star-like SDS are that employing n-Butyl Lithium or s-butyl lithium are that initiator, hexanaphthene are the polymerization system of solvent.But, when the SDS total molecular weight is 5-30 * 10 ⁴, the styrenic consumption is 30-50%(weight) time, the set deformation volume of product is very easily greater than 30%.Thereby when SDS was used as the footwear sizing material, the dimensional stability of footwear was not good enough.

This patent adopts and add few butadiene 0.01-5.0%(weight in the first step styrene polymerization) (is benchmark with the total consumption of divinyl), can synthesize tension set＜30% and not influence the SBS of other physical and mechanical propertiess of product.

The used specifications of raw materials of this patent: styrenic is through underpressure distillation and drying, water number content 10-20PPm; Divinyl is industrial polymerization-grade; Hexanaphthene is collected 80 ° ± 0.5 ℃ fraction through distillation, dry back water number 10PPm; The initiator butyllithium is an own product; Anti-aging agent: 2,6 di tert butyl 4 methyl phenol.

Initiator that this patent uses can be n-Butyl Lithium or s-butyl lithium; As adopt n-Butyl Lithium then should add a small amount of activator, and as: tetrahydrofuran (THF), triethylamine, diethylene glycol dimethyl ether, Tetramethyl Ethylene Diamine, HMPA etc.Usually adopt tetrahydrofuran (THF).

The used styrenic amount of this patent product is that 30-50%(is a benchmark with the total monomer amount), Dui Ying conjugated diene consumption is 50-70% with it.

The molecular-weight average of the SDS that this patent is prepared is 50,000-300,000.The polymeric reaction temperature scope is 40-120 ℃; Polymerization reaction time: 1-10 hour; Monomer concentration is/100 millimeters of 5-20 grams.

In the two phase structure of SDS segmented copolymer, the polystyrene type microcell is the principal element of SDS high-tenacity; Under big external force effect, the stress of elastomeric network polyhutadiene is delivered to the polystyrene type microcell, and this microcell has surrender and distortion ability, before reaching maximum stress, absorbs and storage elastic energy delayed crack.After external force was removed, this non-being heated of distortion that produces owing to the polystyrene microcell among the SDS can not be recovered.This irreversible deformation amount will increase with the increase of polystyrene content, makes this material cause higher set deformation volume inevitably like this.

This patent is intended to not influence under the prerequisite of integrity of polystyrene type microcell, a small amount of conjugated diolefin is inserted in the stiff chain of polystyrene type, make it to have suitable kindliness, do the time spent being subjected to external force, the distortion of polystyrene type microcell can be born by the snappiness that the conjugated diolefine hydrocarbon segment the produced distortion institute that has kindliness on a small quantity partially, like this, just reduced the distortion deformation of polystyrene type, thereby, also just can reach the purpose that reduces the SDS tension set.

This patent finds that a small amount of conjugated diene is inserted into the position of polystyrene segment, and the set deformation volume of product is had bigger influence.This patent has carried out the adding mode of following three kinds of conjugated dienes:

1. a small amount of conjugated diene gives with styrenic and adding in the polymeric kettle after elder generation is mixed again.

2. a small amount of conjugated diene adds after 0.2-5.0 minute in styrenic polymerization reaction.

3. a small amount of conjugated diene adds after 0.5-12 minute in styrenic polymerization reaction.

To the adding of a small amount of conjugated diene, this patent utilizes the reactivity ratio of conjugated diene much larger than the vinylbenzene reactivity ratio, and the mode that adopts polystyrene type to add behind different polymerization times realizes.This patent confirms that under the condition of different polymerization temperatures and monomer concentration, conjugated diene is incorporated as after 0.2-15 minute with the polystyrene polyreaction, preferably adds after 0.5-6.0 minute.Because the conjugated diene amount that adds is so few effect that is separated that does not consequently have influence on product, the physical and mechanical properties of product is excellent.

Employing a small amount of conjugated diene that this patent provided is inserted into the method for polystyrene type molecular chain, and the product set deformation volume can be reduced to 20%-30%.And do not add set deformation volume＞40% of conjugated diene.Thereby, the product set deformation volume is descended one times, and other physical and mechanical properties of product does not change.

This patent has following advantage:

1. the conjugated diene consumption is few, takes conveniently, can be provided by the conjugated diene monomer of this polymerization system.

2. it is simple and easy to do that a small amount of conjugated diene adds mode.

3. can reduce the set deformation volume of product significantly.

4. the adding of a small amount of conjugated diene does not influence the two-phase separating effect of product, and other physical and mechanical properties of product is unaffected.

Insert a small amount of conjugated diene in the polystyrene molecular chain, the problem that should extremely think better of beyond doubt is because the high slightly integrity that will influence the polystyrene chain structure of conjugated diene consumption.This patent is pointed out: the conjugated diene addition is: 0.01-5.0%(weight), optimum amount is: 0.05-1.50%(weight) (is benchmark with the total consumption of conjugated diene) can achieve the above object.

Physical and mechanical properties according to the synthetic SBS of method institute that this patent provided is: set deformation volume:＜30%, and tensile strength: 260～290 kilograms per centimeter ², specific elongation rate: 700～800%, 300% tensile modulus: 33 kilograms per centimeter ², shore hardness: 88.

Example 1

1. the preparation of segmented copolymer

Adopting volume is the medical glucose bottle of anti-chewing-gum skin plug 500 milliliters have, and through heated baking (120 °～150 ℃), and with high pure nitrogen vacuum pump drainage three times, each 15～20 minutes, cool to room temperature was standby under the protection that high pure nitrogen flows then.The first step polymerization process is: add refining hexanaphthene 252 grams successively, vinylbenzene 20.8 grams and tetrahydrofuran (THF) 0.05 gram.It is that 60 ° ± 2 ℃ oil bath electrothermostat gave heat 10～15 minutes that polymerization bottle is placed temperature, remove impurity in the polymerization system with the concentration known n-Butyl Lithium, add n-Butyl Lithium 1.39 mmoles then at 60 ℃ of following initiated polymerizations, and shake polymerization bottle frequently.After polyreaction is carried out 1.30 minutes, add quantitative divinyl (seeing Table 1) with withstand voltage peace pipe rapidly, the color of polymer fluid becomes light yellowly by orange red, shows to have generated the polybutadiene lithium living chain; Change into orange redly behind certain hour again gradually, show that the divinylic monomer polymerization finishes, the intact vinylbenzene of unreacted is proceeded polymerization.Polymerization time is about 1 hour.The second step polymerization process is: be pressed into polymerization-grade divinyl 31.2 grams with high pure nitrogen, and use high pure nitrogen ftercompction to 1.1～1.2 pressure (gauge pressure) immediately, placing temperature again is 60 ℃ of oil bath electrothermostats polymerization 1 hour, and shakes polymerization bottle frequently.The 3rd step coupling process: add silicon tetrachloride 0.417 mmole at twice, 60 ℃ of coupling temperature, 30 minutes coupling time.Reaction ends and adds the anti-aging agent 2.6.4 that is equivalent to polymer weight 1%.Then the polymkeric substance that condenses glue white with ethanol promptly gets translucent product after vacuum-drying.

Above-mentioned experimental data is listed in table 1

2. the test of product physical and mechanical properties:

The physical and mechanical properties of prepared segmented copolymer is as shown in table 2 after tested.

^＊1 HGB 4020-60

^＊2 GB 528-65

^＊3 GB 528-65

^＊4 GB 528-65

^＊5 GB 531-65

Can clearly see by table 2: according to this patent test number NO.1.2.3.4 with 5 prepared products have lower set deformation volume (＜30%) and than excellent physical and mechanical properties.Test number NO.6 and 7 shows: when the few butadiene consumption was too much, though the product set deformation volume is low, the tensile strength of product and specific elongation rate descended to some extent.

Example 2

The preparation method of product and the test of physical and mechanical properties are with example 1, and difference few butadiene in the first step polymerization process gives with vinylbenzene and carries out polyreaction again after elder generation is mixed.Experimental data sees Table 3 and table 4.

Table 3

As shown in Table 4, few butadiene and vinylbenzene add simultaneously, because the reactivity ratio of divinyl substantially exceeds vinylbenzene, make few butadiene preferentially carry out homopolymerization and fail to be inserted in the segment of polystyrene, thereby make the set deformation volume of product fail to reduce.

Example 3

The preparation method of product and the test of physical and mechanical properties are with example 1, and difference is that the adding of few butadiene in the first step polymerization process is after styrene polymerization reacts 2.8 minutes.Concrete data see Table 5 and table 6.

Table 5

As can be seen from Table 6, the product set deformation volume prepared by this example can be controlled between 30～35%, the set deformation volume decrease to some degree.

Comparative example: 1

The preparation method of segmented copolymer and the test of physical and mechanical properties are with example 1.Difference is not add few butadiene in the first step polymerization process, and it the results are shown in Table 7 and table 8.

Table 7

The mensuration of product second-order transition temperature (Tg):

The mensuration of the product Tg of this patent preparation is to adopt Japanese company of science to produce " differential thermal analyzer " (DSC) (standard type).Dryly be: heat-up rate: 30 ℃/minute as condition; Chart drive speed: 20 millimeters/minute; Use liquid nitrogen cooling in the air.Data are as shown in table 9.

Table 9

By the product Tg analysis revealed that table 9 provided, this patent does not have influence on the two-phase separating effect significantly about reducing the tension set method of segmented copolymer.

Claims (4)

1, in order to reduce SDS segmented copolymer (S: styrenic, D: set deformation volume conjugated diolefin), this patent is confirmed: for styrene content is 30～50% (weight), conjugated diolefin is: the line style of 50～70% (weight) or star-like SDS, adopt a small amount of conjugated diolefin monomer methods of adding in the vinylbenzene of the first step polymerization process that this patent provided, wherein a small amount of conjugated diene consumption is: 0.01-5.0% (weight) (is benchmark with the total consumption of conjugated diene), optimum amount is 0.05-1.50% (weight): the joining day of a small amount of conjugated diene was advisable with styrene polymerization reaction in the first step polymerization process in 0.2-15 minute, be preferably in the styrene polymerization reaction and add after 0.5～6.0 minute, can reduce about one times of product S DS tension set.

The method of the reduction product set deformation volume that 2, this patent provided is applicable to and adopts n-Butyl Lithium or s-butyl lithium to be initiator, to be prepared line style of solvent or star-like SDS with the hexanaphthene.

3, the molecular-weight average of the SDS that this patent was suitable for is 50,000-300,000.Polymeric reaction temperature is 40 °-120 ℃.Polymerization reaction time is: 1-10 hour, monomer concentration was/100 milliliters of 5-20 grams.

4, by set deformation volume＜30% of the SDS of method that this patent provided preparation, and other physical and mechanical propertiess of SDS are unaffected.