DE1545126A1 - Process for the preparation of polymeric compounds - Google Patents

Description

The invention relates to a new class of polymeric compounds, which contain novel cross-links between carbon atoms and a new process which ionizing Radiation used to make such connections *

According to the prior art, polymers are used in chemical Method Lm generally about carbon-carbon bonds networked. Of polymers which contain the -Ii-0-R bond, such as polymers and / of copolymers of ethylene oxide and propylene oxide, it is not known that they are united ... crosslinking via carbon-carbon bonds, self hoi application of chemical Measures, are accessible.

One object of the invention is the production of new polymeric substances which contain crosslinking carbon-carbon bonds in the oC position to the oxygen of an ethsai * group.

Another object of the invention is the production of new macromolecular polymeric substances, which in water and organic

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see liquids are insoluble and which are intra- and intermolecular contain crosslinking carbon-carbon bonds; these polymeric substances are stable in the presence of oxygen

Another object is the production of new gel-like substances, which have a structure that in the presence of Oxygen is satbil and consists of polymeric substances, which cross-linking intra- and intermolecular carbon-carbon bonds contain, the structure reversibly enclosing large amounts of water.

These new polymeric compounds contain at least one of the following structural units, said structural Unit is stable in the presence of oxygen:

.— C

H H

A.

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R and R each correspond to hydrogen or a methyl radical, provided that either R or R is hydrogen

YES

is. R. and R. each correspond to hydrogen or a methyl radical, provided that either R or R. is hydrogen.

These new compounds can also be crosslinks via carbon between straight chains and carbon atoms Carbon atoms since label enetändiger methyl groups as well between carbon atoms of this methyl group itself. In addition, a very small and insignificant number of Bonds include two oxygen atoms attached to the carbon atoms.

These bonds can contain crosslinking bonds, which are called intermolecular bonds (i.e. bonds between two

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different molecules) and intermolecular bonds (i.e. Bonds between carbon atoms of the same molecule), exist, as well as combinations of cross-linking intra- and intermolecular bonds.

The term "networking" becomes the definition of that here Process used in which a new carbon-carbon bond is linked in an organic polymer. The bond can be two carbon atoms of two different polymers or link two carbon atoms of its polymer.

The process for preparing the new compounds relates to the preparation of a homogeneous aqueous solution of at least one of the water-soluble compounds of the general formula:

- 0

C.
H

R.

C H

-R-

/ n

where R ₁ and R _{3 are} each hydrogen, alkyl radicals or alkyl-substituted aryl radicals, R always denotes hydrogen or a methyl radical and η denotes an integer which is greater than

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is greater than 1. The solution is then exposed to ionizing radiation treated for a time sufficient to cause a change in the viscosity of the solution. In the end the water is removed from the solution and the residue is recovered * The residue contains polymers which contain the crosslinking bonds described above *

Ionizing radiation in the context of the invention such alpha and beta Feilchen be understood that have a sufficiently high energy content, in order to detach at the immediate past passage in close proximity of atoms shell electrons of the atoms · DLuse alpha and beta Tmilchen cause direct ionization of atoms »

Gamma rays and X-rays do not consist of particles and do not carry any electrical charge, but the passage of Liu through matter causes indirect ionization by knocking electrons out of the atoms. These secondary electrons in turn ionize like beta particles.

For the specific purpose of describing the invention and in the appended claims, the term "ionizing radiation" applies to alpha and beta particles, X-ray and Gamma rays, as well as electrons from Van de Graff and other

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their high-voltage accelerators, applied. The initial solution generally shows an initial decrease in viscosity after irradiation. As the irradiation progresses, it increases the viscosity of the solution above the initial value and further Irradiation creates a macromolecular, gel-like substance.

It is believed that the irradiation of water has the following reaction triggers:

HO H ¹ + .0H

The by the interaction of the ionizing radiation with Hydrogen-Hydroxy! Radicals produced by water can affect certain Types of organic compounds react »A general one Reaction is through the detachment of a hydrogen atom the radicals, where either HO and a substituted carbon off-radical arise * Two of these carbon radicals can combine to form a new carbon-carbon bond or crosslinking bond.

The initial drop in viscosity can be due to a combination of crosslinking and degradation, or to crosslinking, which the shape of the molecule with a reduction of the MoIe-

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changes in volume · The viscosity begins to increase after the number of cross-linked molecules has increased significantly.

Continued exposure may cause formation a sufficient number of crosslinking carbon-carbon bonds that transform the solution into an insoluble one cause gel-like material. The structure of the gel-like substance consists of polymers of the starting materials, which intra- and / or intermolecularly upwardly facing structure and crosslinked to a sufficient extent to form a macromolecular material. The water is reversibly retained in the interstices of the high molecular weight substance. In addition, the crosslinked structure can contain interwoven polymers of the starting materials which are not included in the crosslinking but are so interwoven with the crosslinked structure that they remain essentially insoluble.

The water can be removed from the structure by various methods, included simple evaporation processes, removed, whereby a tough, elastic material is created; this can absorb water in a reversible manner on contact with water, and in amounts which correspond to the initial capacity of the gel-like material obtained from the continued irradiation of the starting solution, approximately equal. The levy

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and absorption of water by the mass can take place in a reversible manner as often as desired.

Starting materials suitable for the present process

are those compounds that contain ether bonds. she

include:

1. Copolymers of ethylene oxide and propylene oxide, which

each contain hydrogen, alkyl or alkyl-substituted end groups and in which the content of ethylene oxide polymer in the copolymer reads between 50 and 75%,

2. Polypropylene glycol, polyethylene glycol, ethylene oxide polymers with molecular weights from 200 to 10 χ 10, and

3. alkyl-substituted phenyl ethers of ethylene oxide polymers, as well as alkyl and dialkyl ethers of polyethylene glycol.

It is preferred that the starting aqueous solutions are free of "radical scavengers". The term "radical scavenger" denotes those types of substances that deal with the reactive React agent, which is created by the irradiation of water, and / or those types of substances, which with the during organic radicals formed during this process react. While very pure water is the preferred solvent for is the starting solution, the presence of small amounts of "radil scavengers" affects the feasibility of this

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BATH

2ü

Procedure not negative; the "Radikuli an.i; ur" react in an early ϋ tat ium of the HeatrahLu; and be may; Lichüi ^v ueiijtä viu needs, so dart si «die arst. fig Verne t cinnamon far e-il; t ι on unhindered t leave very little there «

Oxygen iJl an I) ei »piel einy " Rad ikaJ tangei u ", dar nut l / ddaöra t ot'V atoimm undl / wdor organic radicals leunim-lj. After kui /, ar Ziiit the oxygen is consumed and l diis Vta .-ntitzuug von Kohlanütot £ / al carbon k ^ iin uiiiöiiiierter vörluif «ju.

The pil-Wüi td "t solution did open ji; ht 1 i" ht iir diu.-iö'j Vurfuhrenu not critical, although the i) i Ldu.i> r _r • lrt. j ς j L <ix L iu dii Mu t, «■ i ii 1; J orf jnliir 1 icliu ί, οιΐ durnh Verwätiü <n <Λιπ) ζαηι \ ϋ solution with a pil 'et ι of about>', () b «ti ν JiL • '■ sjrkut t \ » yrdön can »

IHt) leiiiperatui i.3t of t anaichl borrowed fm liö performs hai kei. ditiie / i / erfaliriJiis also not ki ii jcii, since da «geiai. ι. ^ e MuLei ImIh in LoHungtäii with Teinpex'aturuii just above tl> j fief "rierpunktea up to the boiling point dor Aua ^ angälöwn ivi, is formed.

Three related process variables, which are the most effective Carrying diiysea V ^ rfahrone billed

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I5A5126

- ίο

WfM should include the dosage, concentration of the dissolved, polyning the starting material and molecular weight of the

The dosage (i.e. * Euargieubsorp t ion) is indicated here in "rails" * One "rad" corresponds to an absorption energy of 10U ergs per gram of treated fabric.

Additional concentrations of the dissolved starting materials in the final solution generally mean that lower doses of radiation are required for the formation of the gelatinous material. An increase in the molecular weight of the ucelo.-ittsn starting material has in general one thing; ι analogous effect on the formation of the gel-like substance forder 1 ichti ^ iit trahluugsdosis.

d found that if the irradiation is continued, U) * i j <dam the procedure described), until the AuamUJ that diu Löjuuje; A gel-like material is transformed, which must be removed gel-like material in 2, sometimes larger amounts Wa i s <ir contains if the concentration of the output Ib 'solution is more tinl is degraded more.

The gelar tieö material is useful as a humectant, The cross-linked, but still soluble substances are the same

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15 / .5 126

Use the dissolved starting material and can also be used as Intermediate product for an effective preparation of the gel-like Substance to be used «The cross-linked and insoluble material is used in the manufacture of the gel-like materials useful·

For a broader discussion of the use of ethylene oxide polymers as a solute starting material in this invention, for the preparation of novel compounds containing the novel crosslinking bonds included herein, a facilitate further understanding of the invention

In the treatment of ethylene oxide polymers by the process described, preference is given to using polyethylene oxide with a molecular weight of 1.10 ⁵ - 3.10, an aqueous starting solution with at least 2.0 percent by weight of polyethylene oxide and irradiating the starting solution with a total irradiation dose of at least 52.0 .10 "talk" used to create the gel-like material ·

Table I contains a listing of the results obtained on irradiating ethylene oxide polymers of various molecular weights under various conditions as indicated to obtain a gel-like end product

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Tabel Molecular Concentrations

weight kicked

Gew.-S

Atmosphere kind of Irradiation

Dosage in rads

1 'V / 3.0x10 " 2.0 V 3.0χΐ0 ^ο 2.6 * 3 α- 3yOxlO ⁶ 2.6 > k Ί? 3, OxIO ⁶ 2.0 > 5 α 3, OxIO ⁶ 2.0 G Λ, ¹ 3, OxIO ⁶ 2.5 7th 3.0xl0 ^b 2.0 a
W. / ι- ' 3, OxIO ⁶ 0.5 9 3, OxIO ⁵ 3.0 10 Α. / 3, OxIO ⁵ 0.5 Λ / 3, OxIO ⁶ BATH 11 3, OxIO ⁶ 2.0 ORlGINA

air

^Ν 2

^Ν 2 air

Air air air air air air

air

X-ray X-ray X-ray

-r -r

■ V

X-ray X-ray X-ray

0.1x10 '2 xlO ⁶ 1.6χ10 ^ί

1.9x10 ' 0.5x10 * 0.3x10 *

1 X 10 ^v

3xio ⁶

0.67x10

Wt -.% H ₂ O in

gel-like material

viscosity

in centipoise

98

97.4
98
98

96.5
97.7
99 '
98
99

98

Gel Gel Gel Gel

brittle gel gel gel gel gel gel

gel

The gel-like material produced by this process using ethylene oxide polymers as the dissolved starting material can be dried with drainage removal will. As it dries, the gelatinous material gradually shrinks and eventually turns into a tough, elastic material of light color over · The anhydrous mass is in water and various organic liquids, such as methanol, benzyl alcohol, Formic acid, acrylic acid, benzene * nitrobenzene, chlorobenzene, m-cresol, o-nitrotoluene, pyridine, morpholine, chloroform, 2-nitropropane and dioxane, insoluble.

The following tables show the Vi <3kositatsabnahm = j of polyethylene oxide starting solutions after initial irradiation and the subsequent increase in viscosity until the formation of the " gel-like substance »

Table II contains the dosage and viscosity of a homogeneous aqueous solution containing 0.1 GeVi-% Polyäthyiöno-jcyd with an initial molecular weight of about 3x10. The solution was irradiated with gamma rays under a nitrogen atmosphere. After diluting the irradiated sample from a concentration of 1.0 to 0.1 wt.

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Tabel

II

Dose in Viscosity in "rads" χ 10 Centipoise 0.0 2.97 1.3 1.42 1.9 1.33 3.0 1.35 3.17 1.40 4.9 1.48 11.0 gel-like

Table III contains the dosage and viscosity of a homogeneous aqueous solution which contained 0.2% by weight of polyethylene oxide with an approximate molecular weight of 3x10. The solution was irradiated with gamma rays in an air atmosphere. 0 to 0.2 wt .- #, the viscosity measurements were performed with a Hoeppler viscometer according to the falling ball method durchgöfuhr t n at 30 C,

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BATH

Table III viscosity Dose in in centipoise "rads" χ 1 1.16 0.0 1.03 2.38 0.94 7.59 0.96 12.5 0.93 49.6 1.12 22.2 gel-like 62.6

To further explain the scope of the invention, a Copolymer consisting of approx. 75 percent by weight of ethylene oxide and 25 percent by weight Propylene oxide in a homogeneous aqueous solution as long as nit Gamma rays irradiated until a gel-like material was formed. The total dose was approximately 15.6 χ 10 "rade".

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Claims (2)

Claims 1. Process for making polymeric compounds at least if a structural unit of the general formula: ll. I R. H H I - c - ο odei ._ whereby II I ^R 3 ϊ_ and R, I ii R, Wasserst off atoms or methyl radicals represent characteristic either R or R ei. "Wa st» he a toff atom i "t NND where R and _{ Vfasseretoffatome or methyl radical means "if" either R ₃ or R _{1 is a} hydrogen atom, ρ © lc e η η ζ ei ν h η et that one i a d u ι c h 0 ^f ; 9 8 ? ^c 1 1 & 5 η BATH aqueous solution of a polymer of the general formula R ₁ - _0, -R, where R and R are hydrogen, alkyl or alkyl-substituted Aryl radicals, R, in each case hydrogen or a methyl radical and η is an integer greater than 1 is exposed to ionizing radiation until the viscosity of said solution changes. 2. The method according to claim 1, characterized in that κ e k e η that the water is removed from the solution obtained by the process of claim. Method according to claim 1 or 2, characterized in that that the starting material is a polyethylene oxide with a molecular weight of 1x10 to 3x10 used 009826 / 19GO k, Process according to Claims 1 to 3, characterized in that an at least 2% aqueous solution is used as the starting material 5 »Method according to one of claims 1 to 4, characterized characterized in that one for irradiating a 4 dose of at least 52x10 "rad" used · 0 0 9 8 2 6/1950