DE2307050A1 - SILICONE COMPOUND - Google Patents

Description

TELEPHONE CO81O BQ 36 82

Shinetsu Chemical Company in Tokyo / Japan

Silicone compound.

The invention relates to silicone compositions with improved properties, especially silicone elastomer base compositions for use in production of silicone elastomers, which are flame-retardant or self-dissolving seeing after the inflammatory condition has been removed, and which ones also high elasticity or ductility with less permanent Exhibit distortion after release of the burden.

Silicone elastomers are in widespread use, however, show a disadvantage the property of combustibility · It is to watch famous "silicone elastomers non-flammable, for example, by adding a kupferhaltigert finely divided * the methylR-henylpolysilüxan substance to a Siliconinasse and a filler contains (US-PS 2 Ö91 033) or by adding a platinum-containing substance to a silicone compound which contains common organopolysiloxane and a filler ( US Pat. No. 3,514,424). However, these known silicone elastomers do not meet the requirements with regard to self-extinguishing and elastic deformability. In particular, the first-mentioned elastomer cannot be obtained undyed with a copper-containing substance, since it is not suitable for coating wires with differently colored coatings. The second elastomer with Gt-hali: on a platinum-containing substance is the heat resistance. aU; c e.-m: the characteristic properties

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of a silicone elastomer, and also the non-flammable » not given enough "

It is also known to use various molding compounds for flanunfest ~ make, such as antimony oxide, add. The addition of such well-known Flame-retardant agents for silicone compounds would, however, provide end products which have the desired typical properties of the silicone conelastomers no longer have.

The invention is now based on the object of creating a silicone composition which moldings with excellent mechanical Provides strength and heat resistance *

This object is achieved according to the invention by a silicone composition _t containing (a) 100 parts by weight of an organopolysiloxane with the following unit formula

^R a ^Si0 4-a

where R st is a substituted or unsubstituted monovalent hydrocarbon and a is a number of 1 _ä 90 to 2.05, (b) 20 to 200 parts by weight of a finely divided silica filler. (c) 5 to 100 parts by weight of finely divided manganese carbonate and (dl 5 to 1000 Tpm (parts per million), based on component a "of platinum or a platinum bond containing this amount of platinum"

The invention is explained below.

It has been found that when a mass _t containing the above constituents (a) to (d) is heated and vulcanized in the presence of a known crosslinking agent, the mass, like ordinary hot-vulcanizable bilicon rubber, is converted into an autschuk-like elastomer with excellent heat resistance and Tear-resistant oil is converted and, if this rubber-like material is La Stonier

30983 5/090 8

shaped into a ribbon, held vertically and its lower end of the Is exposed to the action of fire, it burns, but goes out by itself after removal of the fire »and that the disadvantage of a permanent distortion when using certain types of crosslinking agents occurs, is largely avoided #

An organo ^ polysiloxane which can be used according to the invention as component (a) is commonly used as the main component of a silicone elastomer matrix and is a straight chain polysiloxane with the. following unit formula

^R a ^Si0 4-a

where R is a. substituted or unsubstituted monovalent hydrocarbon radical, namely a methyl, ethyl, propyl or phenyl group, halogen-substituted hydrocarbon group, vinyl or allyl group or the like and 'a is a number from 1.90 to 2.05 is.

PUr the purposes of the invention, the component (a) has a viscosity 100 000 CS (measured at 25 ° C) should particularly preferably above 1 million CS · This ingredient may be in its structure CH ₃ SiO ₁ containing units, as far as their The amount is small, namely, less than 5 mol%. In addition, this component can have hydroxyl or trimethylsilyl end groups.

As component (b), finely divided silica filler, known killers commonly used for silicone rubbers such as fumed silica, precipitated silica, quartz powder and kieselguhr can be used. The filler (b) is preferably so finely divided that at least 90 % have a grain size below 50 μm (microns). If too large an amount of the component (b) is added, the physical properties of the silicone rubber obtained by vulcanizing the composition are deteriorated.

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Palls the amount of component (b) au is small * the mechanical ones Properties such as tensile strength of the silicone elastomer obtained correspondingly, according to the invention, component (b) should be used in an amount of from 20 to 200 parts by weight for 100 parts by weight of component '(a) are discarded, such as mentioned above"

The finely divided manganese carbonate used as component (c) according to the invention, in combination with the below-mentioned component (d), gives the silicone elastomer excellent self-extinguishing and flame-retardant properties since it evolves carbon dioxide and has a catalytic effect when heated. It has been found that this constituent (c) also greatly improved the elastic deformation of the resulting particles. As in the case of constituent (b), this constituent (c) is preferably so finely divided that at least 90 % of it is one particle size below 50 jn.m (microns) .. In order to obtain such a high flame resistance and high elasticity without deterioration of characteristic properties of the silicone elastomers, this component (c) must be in an amount of 5 to 100 parts by weight ρτο 100 parts by weight of the component "(a) be used *

Looking only at the puncture of the evolution of carbon dioxide gas, one could assume that calcium carbonate zinc carbonate, Cobalt carbonate, sodium carbonate and the like for the purpose of Invention similarly effective selenium However, by adding this Carbonates do not retain the self-extinguishing effect in elastomers and in addition, these carbonates have an adverse influence on the heat resistance of silicone elastomers and can therefore cannot be used for the purposes according to the invention.

The component (d). is required to make the silicone rubber compound

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in combination with the above-mentioned component (c) to impart the self-extinguishing property. As a usable as a component (d) platinum compound may be mentioned platinum chloride and complexes of platinum chloride with alcohols, ethers, aldehydes, etc. Ss is also possible to use as component (d) Products that PlatiEpul- ver on a carrier such as alumina _a Silica gel and asbestos _$ included «

In order to advantageously achieve the purpose of self-extinguishing properties, according to the invention the amount used as component (d) should be 5 to 1000 ppm (parts per million), calculated as platinum metal, preferably 10 to 100 ppm based on 100 parts by weight of component (a),

The erfindungsgeirtäße silicone Sasse can starch forms _g * heating ?, be processed into various molded νηά vulcanizing articles-. Known crosslinking agents (Vt & kanisatiensa & italK iris organic peroxides wad Organoky ^ ogeR-Pelysiloxan © wer-dea ^ mvzwgs "* weise zum Vulkanisiere" 3 ": e strzin & niigs &m'iB& i Masss?: ·. Ώεϊ®γ! R ^ lrmexi used as examples .-ihsr Ps ^ Kclda sei ^ a gmsmit ISeiassyl "peroxide, tert""- Butylperben.zoat # Ss ^ öisälorbeisöylps-Qsicli Di-tert." butyl peroxide, Oicumylperoxid w-iä Monssfel ^ steaeylpayesddi Ba examples for the Organahydrogen? siysiathydrogen? at least two Si "H" bindings ia si ^ sm molecule, .sls lsi case of organic peroxides ψ ^ νά ^ η they ■ ^ föyaiagweise in ©: 'Äar 0.3 to 6 weight steep, ■■ - * prc 100 GewichtsieiXe des Bsstsnilteili; (a) inserted. Furthermore ■, * ::. * T: e I ^ case of ¥ e? ^ Fönaimg ^ i ^ m ^ i "aaö% € ^ 9gen" polysiloxane ü ^, ^^ t ^ ege so ^ 3u ihlt s © iÄ that the gati, cf © rss Si-H 'l.xttduns, ^Ti ..U ^f ic ^hi? _"?' - * ·" * - ϊιό as Si -'- 'Sii ^ Hft ^ BiiiclisK ¹ '': 'i ^ n Bestsmelteil (a) is _# der: Ιϊ- ■' .i.fcy.ei? 'Ä;11' ^ saigstcas ^ / - jd BimdiMgcss- s Si ^ GKcQH ₀ in one through-? ; v * i ^ tl.lmh ^ i McJ.aMi.! © ϊϊί ^ άΐΐέΐ.

Is according to the invention © Silicoasaasse "came *, are prepared" by the above-mentioned ingredients wad mixed (a) Ms (d) the mixture through cm & th to orphan öüqt similarly homogenized. Hach requirement can bucket sQlühen Hass © the blushed organic per-. oxide or Cteganohydrogenpolysiloxan ~ i $ id also a low molecular weight organic silicon compound, such as Dipkenylsilandiol "Diphe" nylmethylsilanol or Alltoxysilaa * pigments "ad other additives are added"

If the thus formed Hass® uat @ r © ^ Äitem Drills odes "Atmospheres" · pressure for several- Sekraidea Ms 1 Sfdo m & B heated about 100 to about 350 ° C νβ & ά if necessary <b & wb & tisuhMAitzw & g imt ^, it becomes a © »G @ f @ rmt © a ^ © dwktg S ₀ Ba © iaar ^ Folieo a volume _ff a baschichtaten eialct ^ ise & ^ a ETOiIt ₀ ^ iallcssaisiertp. which ia different Hisisielit amsgtis @ i € to (it <a lig®aselia £ tea shows _p for example WämebestlMlgissdto S © 3, bit3. ^ seteÄgseig @ asetoFt and. Kautschtakelas ti si tat «

The Erfiiaduiag will i / ai-tex ⁵ © ^ llut ^^ t diseeli the f © ig®M®a examples _ö wherein all ¹³ TeIIe ^ sieii ®ΐΐ? Sswiefet 1sspi @ fe © iio Di © W © ^ te fte hardness ₉ elongation a train £ sstiglc @ it iMd M-sifeead © Id ^ geryisig are aiweli corresponding measuring instruments

norm JIS £ 6301 e ^ liaitsBo Μ® Isögebslg © sigeteft. follow mirde siaek « the method

A sample of the must © wisjtl® imtdi ³ D ^ iasls @ 5i'laitst i «d sm © is® ??

schiakfelie iiit diaes ⁵ Mels® ^ @ ai ea

wurdea- Brüfstüel? © iüit © iadS ³ B ^ dit® vqü 0 _p 5 g @ rad ®1 & @ ΐ "

iwid atm flaiüi © «siiatis ⁰ Ällsöteiassp ©. wsfii vj ^ d ^ t ^ Ibas ¹ nits € © a tsai ^ part € @ s ^ © .feastüeks 15 s @ livmüm ismg ia ler-tlteviaf f © b3? aekt ₀ um © s

and the time until the flame was extinguished was measured. The extinguishing property is expressed as the time (seconds) _t the until _; Extinction passes

example 1

Sine silicone elastomer base material consisting of 100 parts of an organopolysiloxane with a content of 99 # 9 mol # of (GIU) ₂ SiO units and 0.1 mol% of CH ₃ (CH ₂ BCH) SiO units 25 parts of fumed Silicon dioxide (trade name "Airgel 200" - e. ¥ z.) T 20 parts of powdered manganese carbonate (chemical purity!

Tuesday
1 «class)» 2.5 parts of wphenylsilanediol as a silicon dioxide dispersant »0.05 parts of a solution of 2 % (calculated as platinum metal) of platinum chloride in butanol, 50 parts of quartz powder with a particle size of about 5 μm and 5 parts of anatase titanium oxide type was mixed homogeneously to two rolls "and the mixed Hasse heated for one hour at 150 ⁰ C · the Hasse thus obtained were homogeneous on per 100 parts of 0.7 parts of a silicone oil paste containing 50% benzoyl peroxide by means of said two orphan admixed "a molding compound to erhaltent the mass for 10 minutes under 30 kgf / cm ² at 120 ⁰ C vulcanized long to obtain a film 2 hours long post-cured at 150 ⁰ C · physical properties of the obtained vulcanized sheet were measured (Table 1) »For comparison ■ a vulcanized film was produced in the same way as above» except that powdered manganese carbonate was not used * The results de The measurements of this comparative product are also listed in Table 1 «

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- 3 ~
Table 1 2307050 Invention product Comparative product Hardness (JIS)
Elongation {%)
Tensile strength (kg / cm ² )
Flame extinguishing (SekV)
(at the first time)
Flame extinguishing (sec.)
(by far) * 55
300
73
3
0 50
320
75
25th
33

* After completion of the flame extinguishing test, the flame became the The alcohol lamp was again brought into contact with the test piece for 15 seconds and the flame-extinguishing properties were determined again

Example 2

A molding compound was prepared in the same way as in Example 1, except that instead of 0.7 parts of the silicone oil paste with 50 % benzoyl peroxide content, 0 * 2 parts of an organohydrogenpolysiloxane consisting of 2 moles of (CH _{3 I 2} (H) SiO ₀ * "units and 1 mol SiOg units was used * the composition was molded au a film and 30 minutes" cured in an oven at 150 ⁰ C * in flame extinguishing test was extinguished, the thus obtained vulcanized sheet after only 6 sec · »while without Comparative product made using manganese carbonate only expired after 35 seconds »

Example 3

100 parts of an organopolysiloxane consisting of 97 # 85 Μοί-ίέ (CH ₃ ) ₂ Siö units * 2 mol% (C ₆ H ₅ ) _g SiO units and 1.15 mol # GH ₃ (CH ₂ «CH) SiO "units, 3 parts of methyltriethoxysilane, 45 parts of abfltuehtes silicon dioxide and 4 parts of diphenylsilanediol were mixed homogeneously on two orphans" and the mixture was heated to 150 ° C. for 3 hours. The constituents given in Table 2 were mixed into the mass formed in this way in order to obtain a molding mass au *

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From this molding material, a film was prepared in the same manner as in Example 1, are listed in Table 2 which Fl ammlösehungseigenschaf th *

Table 2

Sample no,

3-1 (comparison)
3-2 (invention)
3-3 (comparison)
3-4 (invention)
3-5 (invention)
3-6 (comparison)

Mass manganese quartz »platinum benzoyl flame (parts) carbonate powder chloride peroxide extinguishing (parts) (parts) (2% 50 % Pas * (sec.)

Solution te parts) parts)

100 0 30th 0.1 1.0 35 100 15th 15th 0.1 1.0 2 100 0 50 0.05 1.0 30th 100 30th 20th 0.05 1.1 0 100 40 ' 0 0.05 1.2 0 100 0 0 0.1 1 * 0 60

Example 4

Molding compounds (samples 3 * 1 * and 3-2 «) were made in the same way vie produced in Example 3 from the mixtures of samples 3-1 and 3-2 of Example 3, with only 1.3% instead of Bewzoylperoxid 2 * 4-dichlorobenzoyl peroxide was used, which is part of the disadvantage shows an increase in permanent distortion in SiXicon rubbers. These molding compounds were kept for 10 min, below 30 kp / cm at 120 C, to produce foils of 2 mm thickness and other panels of 12 mm thickness « The latter were used to measure the permanent distortion »

These slides bssv. flatten were post-vulcanized for another 4 hours * at 200 C « TUe measurement of their physical properties provided

in
the values given in Table 3

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2307050 Table ^ PxoU 3-1 ' Pxofce3 «2» (Comparison) (Invention) 57 62 350 320 83 85 50 18th 30th 3

Physical Properties -

Hardness (JIS)
Strain (%)

Tensile strength (kg / cm)
permanent distortion
Flame extinguishing (sec.)

The percentage of permanent distortion is determined by

- V 100 »where A is the original thickness of the material and B the A.

Thickness of its part that does not recover after the stress is removed * are·

Example 5

100 parts of a diraethylpolysiloxane consisting of (CHg) ₂ SiO units »30 parts of precipitated silicon dioxide, 5 parts of methyltinoxy« silane »30 parts of powdered manganese carbonate» 0.1 part of a 2 % solution (calculated as platinum metal) of platinum chloride in 2- Ethylhexanol and 3 parts of a paste containing 50% benzoyl peroxide were mixed homogeneously on two rollers to obtain a molding compound. "This was ^{molded at 120 °} C. under pressure to obtain a film of 2 mm thickness." 150 ⁰ C post-vulcanized. The vulcanized film obtained was subjected to the above flame test. It was found that it did not ignite at all

Example 6

For comparison, the procedure of Example 1 was repeated, except that the powdered manganese carbonate was replaced by sodium carbonate, calcine carbonate or zinc carbonate. The results are * The sample films were further heated 24 hr. At 250 ⁰ C "after which their hardness, elongation and tensile strength loading shown in the following table

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were correct · The results are also in the table a

give.

Tabel

Hangan ··
carbonate Sodium*
carbonate Calcium
carbonate Zinc-
carbonate Hardness (JI3) 55 57 53 Elongation (%) 300 295 330 tensile strenght
(kg / cm *) 73 ■ ■ 77 56 Flame extinguishing j
(SekO

at the first time the second time

After 24 hours at

not a good one

slide was received

away

Hardness (JIS)
Elongation {%)

tensile strenght
(kg / cm2)

220

60
170

66

5 35

75

90

It was also observed that "the zinc carbonate-containing ■■■ which initially showed excellent flame extinction" quickly lost "S: i ^ m property" after being lit several times "while its heat resistance was remarkably poor and the permanent distortion about 3 times as large as the film containing manganese »carbonate»

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Claims (1)

1 · silicone composition containing essentially (a) 100 parts by weight of a grganopolysiloxane of the general formula T, ■ where R is a substituted or unsubstituted monovalent hydrocarbon radical and a is a number from 1 * 90 to 2.05, (b) 20 to 200 parts by weight of a finely divided silicon dioxide filler j (c) 5 to Λ 00 parts by weight of a manganese carbonate and (d) 5 up to Ί000 ppm, based on the weight of component (a), of platinum or a platinum compound containing this amount of platinum. 2 »Silicone compound according to claim 1» characterized in that at least 90 % of component (c) have a particle size of less than 50 yftm * "That the ingredient (d) is present in an amount von.10 3 x silicone composition according to claim 1 or 2, characterized ppm to 100th 4 · silicone mass according to one of claims 1 to 3 _S characterized in that it also contains as constituent (s) Q ₈ , 3 to β parts by weight of an organic peroxide * 5 * Siliconmsisse according to one of Claims 1 to 3 «consisting of (a) 100 parts by weight of an organopalysiloxane with the general formula where R is a substituted or unsubstituted monovalent hydrocarbon radical and a is a number from 1 * 90 to 2.05 _p with a content of at least two "Si" CH "CH _g "bonds; a in an average molelciuaj (b) SO up to 200 parts by weight A finely dispersed silicon dioxide filler SiCc) 5 to 100 parts by weight of a gas content f (d) 5 Ms 1000 ppm. (TsjJe p: vo Killicn) 309835Λ0908 the weight of the component (a), containing platinum or such a quantity of platinum platinum compound and (e) an organohydrogenpolysiloxane in an amount such that the number of ASSI-H bonds 0.8 to 1 ₁ 5 per * Si-CH = CH ₂ -Bindtöigen in component (a) is * 309835 ^ 0908