JPS60115604A - Polymer having functional end and manufacture - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] (Industrial application field) This invention relates to polymers with functional ends.

This invention relates particularly, but not exclusively, to polymers referred to as liquid rubbers, i.e. polymers having a glass transition temperature ('rg,s)' substantially below room temperature.

(Prior art) Liquid rubber having a functional end can be used as a sealant, a coating material,
Used in many applications including lubricants, elastomers, foam materials, and solid rocket propellants. Liquid rubber itself often has a low molecular weight (typically 1000-500
o) However, the presence of two or more reactive functional groups at the polymer button end makes these liquid rubbers suitable for the production of high polymers by reaction with other polyfunctional reactants. ing. For example, a dihydroxy-terminated liquid rubber can be reacted with a diisocyanate to form a polyurethane, reacted with a diacylnolide to form an all-polyester, or reacted with a soepoxide to form an all-epoxide. can.

The fluidity of this rubber is important in that it allows the handling of reactants at ambient temperature, and this is important in automated operations, such as reaction injection, where both components of the process must be liquid at room temperature. Particularly preferred in formation.

However, commercially polymerized lacquer liquid reactive rubbers are based on feedstocks obtained from fossil fuels, such as butadiene from oil.

PROBLEM SOLVED BY THE INVENTION The present invention provides functionally terminated polymers that are obtained from reproducible feedstocks and that can be produced in a simpler Hiko technique than currently available liquid rubbers. The purpose is to

(Means for Solving the Problems) According to the present invention, a terpene or its oxygen derivative having a double bond or a conjugated double bond that can be used for polymerization is used to form a desired functional end for a polymer. A polymer having a functional end obtained by polymerization with an initiator having a group providing the desired end or a group used to generate the end is provided.

The polymers of this invention have terminal functional groups that are the same as those present in the u11 initiator or are derived from groups present in the initiator.

The terminal functional group is, for example, a hydroxyl group, an amine group, or a carboxyl group. This end group allows the polymers of this invention to react with other components to provide elastomers, sealants, adhesives, and also to be used as rubber tougheners. For example, the polymers of the invention with terminal hydroxyl groups are used to produce polyurethanes or polyesters.

The terpenes (or their oxygen derivatives) used in the production of this polymer have double bonds or conjugated double bonds that can be used for polymerization, i.e., one in which steric hindrance does not prevent the merging. It is something.

Oxygen derivatives of chiluin that can be used include ketones and aldehydes. In the following description, references to terpenes are understood to include oxygen derivatives.

Preferably, the terpene is an acyclic, monocyclic or binomial monotylpente having 10 carbon atoms. Examples of suitable terpenes are listed below.

Hereinafter, all white acyclic monotylated hydrocarbons α-myrcene, β-myrcene (α-Myrcene) (β-Myrce
ne) (4-cis-6-cis-Allooclmene) Acyclic monoterpene hydrocarbon Dihydromyrcene (Limonene) (4), pentene) (1,8-p-Menth
monocyclic monoterpene hydrocarbon trans-iso-Limonene carvone
Carbone (Iso-Pulegone)
Bicyclic monoterpenes α-pinene β-pinene (β-Pinsna) Most of these terpenes are readily available from the paper machining industry and the fruit processing industry, or in the case of myrcene and ocimene. can be easily produced from the above-mentioned terpenes. For example, myrcene can be obtained in high yield by pyrolysis of pinene. Therefore, the method described in this specification:
This is particularly advantageous in the Sesheng region where terpenes are readily available but oil-based feedstocks are expensive.

The polymer of this invention preferably has a molecular weight of 500 to 20,000.
and is most preferably a liquid rubber, ie, has a Tg's well below room temperature. Such liquid rubbers may be prepared by polymerizing an acyclic monoterpene or a mixture of cyclic monoterpenes containing 10% or more acyclic monoterpenes (more preferably 50% or more acyclic monoterpenes). is given by Preferred acyclic monoterpenes for preparing the polymers of this invention are β-myrcene and cis-α-ocimene.

Generally, the method used to convert terpenes to the polymers of this invention involves the production of the polymer through the use of a suitable initiator, preferably a free radical initiator or an anionic initiator.

The initiator may contain, for example, hydroxyl, carboxyl or amine groups to provide a functional end to the polymer bulk. The chain termination step of the polymerization reaction ensures that the resulting polymer has functional groups at both ends of the chain. Alternatively, the initiator can be selected to contain groups that, when introduced into the polymer, are used to generate the desired functional end.

Although the invention will be further described with particular reference to the production of terpene polymers having terminal hydroxyl groups, polymers having other functional groups could be similarly prepared.

For the production of polymers by free radical methods, initiators preferably containing hydroxyl groups,
For example, hydrogen peroxide or hydroxy-substituted azo initiators are used. Then, polymerization proceeds through the following route.

Diols are formed by combinations of hydroxy-terminated polymer radicals and initiator radicals or by coupling reactions.

Another method is to form a living polymer using the appropriate radical anion, then add the required amount of monomer, and finally form the hydroxyl groups by adding an epoxide or aldehyde.

A feature of this invention is that the reaction can be carried out at atmospheric pressure due to the intermediate boiling points of the monoterpenes.

This is a distinct advantage over butadiene and isoprene polymerizations which are carried out in closed vessels.

The polymerization is carried out in the presence of an initiator and a bath for the monomers. Suitable solvents include alcohols such as isonoronol, alcohol, n-butanol and pentanol, and polar aprotic baths such as acetonitrile and dimethylformamide.

It is imperative to note that the solvent should be non-reactive with the reactants and products. Namely, Cal? In the preparation of xy-terminated terpene polymers, alcohol should not be used as a solvent because of the formation of ester functional groups.

The exact choice of solvent will depend on the particular initiator system used. For example, polymerizations using hydrogen peroxide or azo initiators are typically carried out at temperatures ranging from 50°C to 100°C. Suitable solvents in this case would be gulo i4nol and butanol, which are sufficiently volatile to be easily removed in the hjH step. If an azo initiator is used, a solvent such as dioxane may be suitable. In anionic polymerizations, non-polar solvents will be used at low temperatures depending on the initiator used. That is,
Tetrahydrofuran, toluene or Haetherda 1 would be suitable solvents.

In a typical case, the selected terpene is dissolved in alcohol with harsh hydrogen and this mixture is
Heat to 00°C for several hours. After this time, the solvent and residual monomers are removed by vacuum distillation. further nt of product
Whether or not it is necessary to produce it depends on the properties of the IF mer.

Some molecules, especially conjugated dienes, tend to form oligomers. For example, myrcene dimerizes through a thermally initiated Diels-Alder reaction to form at least four persimmon products, which, if present in significant quantities, can be extracted using simple extraction techniques. It would be desirable to remove such products.

Examples of the process of this invention and some uses of hydroxy-terminated liquid rubbers are then presented in 8d.

Margin example 1 below. Manufacturing of hydroxy-terminated polymyrcene Industrial grade myrcene was first evaporated in vacuum to remove polymers formed during storage. This myrcene of 200- (also φ-
and L-limonene, and myrcene (approximately 80 g) per 1
The mixture, mixed with 33 me of n-butanol and 20 ml of 50% hydrogen peroxide and contained in a 1 t flask with a long condenser, was flushed with nitrogen for 30 minutes and then heated to reflux. Refluxing was continued for 7 hours and the mixture was then rotary evaporated to 9
4. The crude polyol of Sl' remained. A small amount of quinone crystals was added to prevent air oxidation, and the mixture was slurried twice with methanol (100 ml), precipitated each time, and the methanol was decanted off. The methanol contained oligomeric material (11,f) with low functionality. The remaining polyol layer was dissolved in isopentane and dried over anhydrous magnesium sulfate, filtered and evaporated to give 80 g of a colorless viscous liquid.

This polyol had the following properties. Equivalence (by acetylation): 1322° Molecular weight (average value) Vapor pressure osmosis (VPO): 2110: Permeation chromatography (GPC): 2300° Polydispersity (by GPC)
=1.75° Infrared spectrum (NaCl silane): 3400
7' a -t, OH-stretch; band present in myrcene without 3100): conjugated double bond C=C stretch without 1600, present in myrcene); 1450
reconnaissance), 13908% 1120m, 840m.

H-NMR spectrum (20% solution in CCt4, 220
■ h, tetramethylsilane internal standard): δ = 5.05,
2 protons on olefin site; 1.97, broad multi-iblet, 8 protons in methylene CH2; 1.6
and 1.53, a total of 6f rotons on the methyl group.

Glass transition temperature (Dubon 990, DSδ1-de, heating rate 20°C/min) -57°C.

10.1 parts of the above polyol containing 0.1 w/w % quinone was constantly stirred with 3.11 parts of 4.4'-noisocyanatophenylmethane (MDI) at 70 tllC in vacuo for 1 hour. It made me react. To the clear viscous liquid, 0.77 parts of 1,4-butanediol was added and the mixture was stirred under vacuum for an additional 45 seconds. The mixture now became milky. This is a flat P
Pour into TFE mold and heat at 100°C for 1 hour, then 8 hours.
It was cured at 0°C for 14 hours. The obtained polymer was a white soft rubber (measured at 23° C. and an elongation rate of 20 w/min). It had a Tg of -56°C and a melting endotherm at 203°C (by DSC, heating rate 20°C/min).

In contrast, the electrolyte produced directly from the above polyol and MDI without chain extension using butanediol is a transparent soft adhesive rubber, which is
0% elongation at break, 0.24 MPa tensile strength, 0.
It had a modulus of 1 MPa.

It had a Tg of -54°C, 17, but no other transition points.

Similar polymers were prepared using the same conditions as in Example 1, except that different hydrogen peroxide concentrations were used.1. Ta. Details are shown in the table below.

1 0.5 3190 4000 4100 1.32
1.0 2260 3400 3400 1.53
1.9 1910 3300 3000 1.64 3
．． 6 1650 3800 3500 2.15 5.
4 1350 3100 3100 2.3* Average functionality When these polyols are reacted with the theoretical MDI, % glues are formed and the glues from trials A1 and 2 are sticky; - Trial JIFA: (.

Glues from 4 and 5 were non-stick. Everything was transparent and pale in color.

Add a small amount (4w/w%) of polymyrsensool to high
It has been found that incorporating K into the rg polyurethane network improves the physical properties. This network structure is M
DT, ) IJ methylolnoropane (TMP), and the oxypropylated triol LIIT240.

4.2 parts polyol, 21.6 parts TMP, and 1
2.2 parts of LHT 240 at 50°C under vacuum
Stir for 0 minutes and then add 68.0 parts of MI)I.

The mixture was stirred for an additional 3 minutes until clear, poured into PTFE molds and cured at 150° C. for 1.5 hours. The unaltered polymer prepared as a control contained 58.5 parts MDI, 10.0
240 parts of LHT and 18.9 parts of TMP under the same conditions as above. These physical properties were as follows.

The following total whiteness Quality - 〇 Rubber - 1 tensile strength (MPa) 79 81 Ultimate strain) 4.8 7.1 Modulus (GPa) 3.0 2.8 Toughness (MPa)
a) 94 156 Tg) 155 153 G・(kJ-2) (b) 1.33 1.48 Appearance Colorless glassy White glassy (a) Area under stress-strain curve (b) Fracture in impact test Energy; G, P, M
Arshall et al., J. Mater, Sci., 8+94
9+ (1973).

30 ml of myrcene (GI, C analysis, 96% purity) was mixed with sooxane (30 ml) and the reaction mixture was purged through a chamber. Azobiscyanopentane M (2,47,9) was added and the mixture was heated at 70° C. for 7 hours.

Then, after adding a small amount of benzoquinone crystals to prevent air oxidation, the solvent and residual monomer were removed by rotary film evaporation under vacuum. The resulting viscous product was then dissolved in n-penkun C (25 ml) and shaken with methanol (150 mA).

The mixture was allowed to stand overnight and the methanol phase was decanted and the pentane phase was dried over anhydrous magnesium sulfate, filtered and rotary evaporated to 13.01
g (54% conversion) of a viscous pale yellow liquid was obtained.

The carboxy wood end polymyrcene had the following properties.

119:1840 (titration of methylene chloride solution with alcoholic potassium hydroxide). Average molecular weight (vapor pressure osmotic pressure method): 4030. Functionality average value: 2.19° Infrared spectrum (NaCt plate) is Myrcene'4Npi
Absence of body (absence of 1600 crn band), 1
720 (>C-0 stretch in -COOH), and small bands at 2250 cm (-C=N).

It should be noted that the solvent used in this example (sooxane) is inert with respect to the reactants and q products. n-
In an attempt to produce carboxy-terminated polymyrcene in butanol (the solvent used for the production of hydroxy-terminated polymyrcene in Example 1), a product containing ester functionality was obtained.

Patent Applicant: The University of Manchester Institute OZO Science and Technology Patent Agent: Akira Aoki, Patent Attorney Kazuyuki Nishidate, Patent Attorney Kazuyuki Fukumoto, Patent Attorney Akira Yamaguchi, Patent Attorney Masaya Nishiyama 1st Continued page @ Inventor John Lawrence UK [Stamford Road 1 @ Inventor John Leslie Power UK “Us -
Nage own Manchester, Flixton, Wood Centro 1M 191 RA, Manchester, Ballane 691

Claims (1)

[Claims] 1. In the method for producing a polymer having a functional end, chiluin or its oxygen derivative having a wheat double bond or a conjugated double bond available for polymerization is used as a functional end for the polymer. A special method in which polymerization is carried out together with an initiator having a group that provides a group or a group that is a precursor of the terminal. 2. The method according to claim 1, wherein the chiluine is an acyclic monoterpene. 3. The ift F non-M monoterpene is α-myrcene,
B'6 consisting of β-myrcene, cis-α-ocimene, 4-cis-6-cis-alloocimene and dihydromircene
The method according to claim 2, which is selected from: 4. Using the oxygen derivative of chiluin, and using diuL (4
4, one of which is selected from the group consisting of aldehydes and ketones;
, 1JV item r4 request range The method according to item 1. 5, 7'l'l WF b cumulative conductor is a ketone,
5. A method according to claim 4, wherein the carbon is transported from the group consisting of carvone and iso-brevone. 6. The method according to claim 1, wherein the terpene is a monocyclic monotyl hydrocarbon. 7. The monocyclic monotyl hydrocarbon is limoney, 1.
7. The method of claim 6, wherein the compound is selected from the group consisting of 8-p-menthadene, and trans-iso-limonene. 8. The method according to claim 1, wherein the terpene is a bicyclic monotylin. 9. The method of claim 8, wherein the bicyclic monoterpene is selected from the group consisting of α-♂ene and β-pinene. 10. The method of claim 1, wherein the reaction is carried out in the presence of an initiator and a solvent for the monomers. 11. The method of claim 1, wherein the initiator is a free radical initiator. 12. The method according to claim 11, wherein the initiator contains a hydroxyl group. 13. Claim 122, wherein the initiator is selected from the group consisting of hydrogen peroxide and a hydroxy-substituted azo initiator.
How to write the section. 14. The method according to claim 122, wherein the reaction is carried out at a temperature of 50°C to 100°C. 15. The method according to claim 12, which is carried out in alcohol as a solvent. 16. The method according to claim 1, wherein the initiator contains a xyl group. 17. The method of claim 166, wherein the initiator is an azo initiator substituted with carboxy. 18. The method of claim 166, wherein the reaction is carried out in a solvent in which Cal is non-reactive with respect to the xy group. ]9. With an initiator having a group that provides the functional IP end of the terpene or its rJ1 derivative conductor polymer with a double bond or a conjugated double bond available for association or a group that is a precursor of the end end. A polymer with a transparent end obtained by polymerization. 1:1. Shimoki Shiro