TW200302834A - Particle-shaped partially or fully cross-linked rubber and its use - Google Patents

Abstract

Particulate, partially or completely crosslinked rubber having a glass transition temperature which is lower than 0 DEG C has network points which are connected to one another by network arcs which have an average molecular weight of from 10000 to 50000 g/mol. According to the invention, the mean nuclear magnetic resonance transverse relaxation time (T2m) of the rubber protons is from 3 to 15 ms when measured at 140 DEG C and has an at least bimodal relaxation time distribution (h(T2)), a first fraction which is at least 70% having a mean transverse relaxation time (T2s) of from 2 to 10 ms. The novel rubber is used in grafted or ungrafted form, preferably as an impact modifier for molding materials.

Description

200302834 发明 Narrow, description of the invention (the description of the invention should state: the technical field to which the invention belongs, the prior art, content, embodiments, and a brief description of the drawings) I. Technical rehabilitation ^ This invention is about granular partially or completely crosslinked rubber And its use, in the form of grafted or ungrafted. Such rubbers can be used, for example, to increase the dent impact strength of thermoplastic or thermoset transfer materials, but they can also be used for other purposes. The present invention also relates to a method for preparing the rubber, and a method for controlling such rubber or a dependent product produced from the rubber. The impact strength of A front plastic is usually increased by mixing the elastic component into the polymeric matrix. This mixing can also be achieved by, for example, copolymerization or graft polymerization. For this reason, elastic polymers are used to increase the concave fe impact strength of thermoplastic or thermoset mold materials. Shaped articles are used in a wide range of applications, such as for domestic articles, automotive components, housings for electronic devices, toys and sporting goods, pipes, etc., and are produced from such reinforced molding materials. For example: ABS polymer is widely used, where the styrene / propionitrile copolymer's impact strength is increased by adding butadiene rubber. This is usually done by graft copolymerization of styrene and propionitrile in the presence of rubber, and if necessary, the subsequent grafting of the grafted product with separately prepared hard components is usually done. Composed of styrene / propionitrile copolymer. For example: This thermoplastic moulding substance is described in European patent application EP 0 022 200 A1. The rubber is added in the form of particles to a matrix formed of hard components. According to European Patent Application EP 0 022 200 A1, if the impact modifier used is a graft copolymer containing polybutadiene as a graft substrate, it has obtained improved impact strength at relatively low temperatures and good Glossy cough substance, and 200302834 ⑺ warming said _: Continued and the grafted shell of styrene and propionitrile is a reduced form, which has an intermediate particle diameter from 0.2 to 0.45 亳 m (overall quality ϊϊ 刀The d50 value of the cloth), the transverse NMR # t ^ _ of the insoluble portion separated from the mold material, and the vibration relaxation time (Ding 2] 11 relaxation time) is from 0 · 7 to 1.5 love: seconds. However, the exchange

The impact strength of rubber at relatively south temperature is still not satisfied for many applications. X Summary of the Invention Because of the double bond contained in the succinyl polymer φ mm and the natural material, ABS plastic is sensitive to light and weather. M nw double bond or rubber modified with low double bond content based on impact modification. Agents are often used in particular for the formation of shaped objects from reinforced mold substances, while the shape: 3 ^ 叩 The shaped objects are exposed to the effects of the environment. In these special examples, polymers based on propylsulfonyl p II μ ^ alkynyl 5a, especially n-butyl acrylate or propyl 1 P #. ^ And inner plate Θ 夂 2-ethylhexyl ester . The corresponding granular elastic polymer, which can be used as an impact modifier in an ungrafted or grafted form, is generally composed of the following components: aOSO-100% by weight alkyl acrylate, having 1-3. Alkyl group of 1 carbon atom and the following component & 2) 0-50% by weight of at least one other monomer copolymerizable with ai). The glass transition temperature of this polymer must be below 0 t, preferably below -i 5 ° C. The term glass transition temperature is understood herein as the meaning of glass transition temperature measured by DSC method (differential scanning card meter, 20 C / min, midpoint) (Reference: ASTM D3418-82). In order to establish the desired glass transition temperature in the preparation of the corresponding polymer, the skilled artisan will begin with a suitable monomer mixture. According to Fox (T. G · Fox, Qiu // Jm · P / Xun, SocJ (Series π) i 200302834 (3) (1956) 'p. 123 and Umenmann's Encyclopedia of Chemical Technology (uilmann's CT ^ mk), 4th edition, volume 19, Verlag Chemie, Weinheim (1980) pages 17, 18), the following is a good estimate of the glass transition temperature Tg of the copolymer at high moles: 1 X1 X2 Xn -----] --- (--j-- ts η τ: ... …… τ; where X1, X2, ..., Xη are the mass fractions of monomers 1, 2, ..., η , and

And T, T2g, ..., but% are the glass transition temperatures of the polymer consisting of only one of the monomers 1, 2, ..., η in each case, measured in Kelvin degrees. The glass transition temperature of homopolymers is known to those skilled in the art, for example: from Umenmann's Encyclopedia of Industrial Chemistry (Ullmann's valence / a / CAem / valence), 50th edition, VDH, Weinheim, A21 Book (1992), 169 pages; or A. The Combination of J. Brandrup and E. H. Inmmergut # f. "Po / 少 mer / ίαm¾oo Fantasy, 2nd Edition, J. Wiley, New York 1975, pp. 139-192.

This granular alkyl acrylate rubber has been used in a propionitrile / styrene copolymer as an impact modifier. These systems are known by the name of ASA and consist of a poly (styrene-propionitrile) matrix (PSAN), which contains, for example: polybutyl acrylate particles, which are preferably grafted with polystyrene-propionitrile. However, the impact strength of known copolymers is still not sufficient for specific applications. Embodiments An object of the present invention is to provide a novel particulate partially or fully crosslinked rubber ' which allows the preparation of thermoplastic and thermosetting molding materials having substantially souther impact strength. 00 200302834

’The search for Shida impact modifiers has been extremely tedious and expensive. Before saying <, you must have a sword / gong, _, and prepare different rubbers for Daxia. In most cases, the particles of the rubber? Are then grafted and subsequently added to the thermoplastic or thermosetting matrix f under defined conditions. An appropriate test species then produces I from the resulting mold material and is tested mechanically. Based only on the results of mechanical studies on the test species, it is possible to assess whether specific rubber particles have caused an improvement in the impact strength of the mold substance. Eighteen people have found that: the purpose is to surprisingly find that the granular partially crosslinked rubber is reached. Its polymer network has a network of foxes, that is, polymer chains between adjacent network points are added to a thermoplastic or thermosetting matrix. In particular, having a specific minimum length and teaching fluidity results in a particularly large increase in impact strength, especially in the recessed impact strength of the resulting mold material. Therefore, the present invention relates to a granular partially or completely crosslinked rubber film having a glass transition temperature lower than (TC, the rubber has a shape point connected in a network shape. In the novel rubber, the network shape, ρ π nw Ding J knife is set from 10 000 to 50000 g / mol, preferably from 1; 3 000 to 40 H_ to 3. _ g / mol. U Wu Er 'special In the case of a given monomer, the average score of the mesh arc Η ::: r amount. There are different known methods, such as this = Yongkou,. Length of the mesh arc of the same road. However, this The reticulated arc is preferably measured by the method of ==: explained in more detail below. Particularly suitable for the two-core magnetic, vibrational methods, especially the measurement of the transverse relaxation time D2,

^ ii itb He ot I provides information on the fluidity of the mesh arc. Gu Fen Er / Yun Ye t ^ It has been found spiritually. Its fen, the arc has a lateral relaxation time that can rubber 1 H core ^ 2m) described as from 3 200302834

With a flowability of up to 15 microseconds, a particularly large increase in impact strength is detectable. The relaxation time must be measured above the NMR glass transition temperature of the rubber

Tg 'was performed at this temperature, and the NMR glass transition temperature was defined as the start of a steep increase in the l (t) diagram. Due to the effective frequency in the kilohertz range, eight is shifted to a temperature higher than the statistically measured glass transition temperature Tg. Therefore, the measurement of the relaxation time must be above the static glass transition temperature of the rubber

Tg is performed at a sample temperature of at least 30-50 c, preferably above 80. [. Measure particularly well at 100 above the still glass transition temperature. It is completed at 0 °, because the dry circumference at this temperature is also called Ding 2 plateau period, and the measured η relaxation time only slightly increases with temperature. Therefore, the present invention also relates to a granular partially crosslinked rubber, which has a glass transition temperature lower than ot, wherein the transverse magnetic relaxation of the 1H core of the rubber can be described by the transverse relaxation time (T &). It is from 3 to 15 leap seconds. However, according to the present invention, a rubber having both a mesh arc length and a lateral relaxation time ^ within the requested range is particularly preferable.

/ The measurement of the transverse NMR relaxation time of a substance (also known as the spin and spin relaxation time) is familiar to those skilled in the art. For this purpose, the needle is the hydrogen nucleus of the polymer chain). For this purpose, the sample of the substance is V-entered into a static magnetic field, which strengthens the preferred direction of the nuclear rotation of the hydrogen nuclei. The # 'magnetism excited at high frequency pulsating resonance is generated perpendicular to the preferred direction by the static magnetic field. As a result of the two-pole interaction of the hydrogen nuclei with each other, the magnetization decreases with time. The time during which the magnetization is reduced to its initial value of j e 4 knives corresponds to the lateral relaxation time I. Therefore, in the simplest case of g, the attenuation of the transverse magnetization can be an exponential function of the time constant D 2 $ -10-200302834

(6) Convergence. However, relaxation methods in polymer networks often show more complex behaviors' which can no longer be described by simple exponential functions. Then the analysis of the percent magnetization of the transverse magnetization can be described by the distribution of the τ2 value. For example, when the two-finger number is loosened, a two-statistic τ2 distribution is obtained. Therefore, the time during which the transverse magnetization is reduced to part e of its initial value corresponds to the average value of different transverse relaxation times, and is designated as T2m in this application. It is known that the lateral relaxation time in polymer networks provides information on chain dynamics and parenting density because the mesh points limit the range of achievable chain morphologies in practice and therefore avoid bipolar interactions about moving hydrogen nuclei. Isotropic mean of action. The lateral relaxation time is therefore an average numerical measurement of the movement of the polymer chain. The lateral relaxation time of 3-15 milliseconds found in accordance with the present invention is surprisingly corresponding to the network topology of rubber particles (t〇p〇1〇gy), which leads to "thermoplastic and thermosetting properties" A particularly superior increase in the impact strength of the mold material. Many advantages are related to the characteristics of this novel polymer. By means of transverse nuclear magnetic resonance relaxation time: nuclear magnetic resonance (NMR) relaxation measurement has short measurement time, good reproducibility, and simple operation of the measuring instrument. E Research does not set special requirements on sample consistency and shape. However, the present invention has special advantages and the fact is that it can even be tested as an modifier of ungrafted rubber to increase the impact of the mold substance ... The superior properties of the impact modifier are determined by Wei Wen ... Geopolymers are very decisive. On the other hand, the measured relaxation time of the right ungrafted polymer is not within the scope of the invention being recognized as superior. In the grafting stage according to the present invention, the result of He Mansi will not be lost. In many cases, further processing steps of the host are thus omitted. On the other hand, the 200302834 ⑺ graft copolymer based on the ^ & granular elastic polymer is a modifier.

Particularly advantageous as a thermoplastic or thermosetting mold material. Therefore, the present invention also provides a graft copolymer, which will be grafted from, cut, and cut. U [main y 9 · 9% by weight of the graft substrate For the preparation, the age range is from 5 to 95% by weight, particularly preferably from 10 to 90% by weight. The substrate is made of the V-new jaw granular partly or completely crosslinked rubber, and the rubber is from 0.1 To 99.9% by weight of the graft monomer, preferably: from 5 to 95% by weight, particularly preferably from 10 to 90% by weight. The grafting monomer is preferably

: Styrene welding, propionitrile, (meth) acrylic acid vinegar, or a mixture of these monomers. ▲ The present invention also relates to the use of the novel granular partially or completely crosslinked rubber and, or: a new-type graft copolymer, to modify plastic mold substances, especially force ..., I | ± or thermosetting mold substances The impact strength of the depression. Finally, the present invention also relates to a thermoplastic or thermosetting mold material, which comprises a thermoplastic or thermosetting polymer from 1 to 99 weights as a matrix, preferably from 5 to 95 parts by weight, particularly preferably from 10 to 9 〇Parts by weight; the novel granular partially or completely crosslinked rubber and / or the novel graft from 丨 to μ by weight

Copolymer, preferably from 5 to 95 parts by weight, particularly preferably from 10 to 90 parts by weight 'and w to 50 parts by weight of conventional additives, insoluble fractions separated from the mold material, When measured at 14t, it has a lateral relaxation time π) from 3 to 10 milliseconds. Depending on the composition, the novel mold substance may have a recessed impact strength of greater than 40 kilojoules per square meter at 23 t, particularly preferably greater than 50 kilojoules per square meter. The sag impact strength was measured according to IS0 179, using an izod test species with a size of 4 mm x 毫米 0 mm 9.2 pen meters, and heated to -12-200302834

In the mold, 纟 270 C is produced by injection molding the mold material. The recessed impact strength described herein relates to a novel mold material that does not include the addition of d ..., and the mold material preferably contains up to 50 parts by weight of conventional additives such as glass fiber specific additives. Negatively affects the dent impact strength, so that novel mold materials containing this additive will also have dent impact & below 40 kilojoules per square meter. The invention further relates to a shaped article containing such a mold substance. The characteristic of this novel granular rubber is not the individual transverse relaxation time, but the distribution of the relaxation time (ML) and relaxation time D2, which are usually expressed in logarithmic level h (/ "T2). The invention begins to consider real The polymer network (colloid) of acrylic rubber has a network arc, that is, the polymer between adjacent network points is different in length and its different fluidity is also reflected in different relaxations. Chain ends, that is, polymer chains that have only one network dot terminal, and shorter segments and monomers that are not added to the network. Free chain ends and free segments (gel solutions) have a particularly high flow rate, And therefore there is also a high T, relaxation BB — " J has found that it is suitable as a polymer that significantly increases the dent impact strength of thermoplastic or thermoset casting materials, with at least a double statistical relaxation time distribution ⑽2) ' Part _ It is at least 7Q% with an average lateral relaxation time T2s from 2 to 10 milliseconds, based on the number of hydrogen nuclei, preferably from 2.8 to 10 leap seconds, particularly preferably from 3.0 to 8 milliseconds .Assumption: This first part is It is defined as the fluidity of the polymer chain-that is, the network arc-fixed by two network points. The second higher flow part ❾ 'can be said to reflect the defects of the polymer network ^ such as: free chain ends And colloidal solution, with an average lateral relaxation time T2f greater than 10¾ seconds. Its proportion is superior to not more than 15%. 5 and (represented by -13-200302834 respectively

(9) Slow and fast 'and means the lower flow (slow) and higher flow (fast) parts, respectively. For the measurement of the direction relaxation time distribution, the skilled artisan can once again rely on many NMR methods known per se. Particularly preferred is the Hahn, s rotation-echo method, in which initially the free-induced decay (FID) is refocused after a certain development time assisted by a high-frequency pulse sequence. The desired T 2 distribution was measured numerically from experimental NMR lean materials. The distribution function h (~ T2) is roughly measured with the assistance of an inverse Laplace transform with a pre-measured basic function. The α number 疋 comes from the magnetic field] y [(t) as a change in the time function. In this case, the exponential function exp (-t / T2) is superiorly selected as the base function. It is assumed that the polymer is sufficiently fluid to cause a purely exponential D 2 decay to each chain. This hypothesis can be simulated experimentally by performing a relaxation test at a temperature much higher than the glass transition temperature of the rubber, for example, about 14 ° in the case of the novel polymer. 〇. The numerical problem is a solution to the first-order Fredholm integral equation, using experimental data contaminated by interference. Business Suite software is available to address this issue. The program FTIKRG from Scientific Consulting Group GmbH (Freiburg) [Fast Tikhorov Scale

Tikhonov

Regularizatum)] can be proposed here as an example. A more detailed teaching of potential numerical methods is found in, for example: Continuum Mechanics and Thermodynamics 1 (\ 99Q, \ 7 'Anti-Computer Physics Communications 6_9_ (1992) pages 99-111. Between two adjacent mesh points The average length of the reticulated arc can be calculated from the mean transverse relaxation time Ding 2. During the Ding 2 plateau period, that is, when the sample temperature is at least 100 ° C higher than the glass transition temperature, between the two reticulated points The average value of the irregular part z can be calculated as: -14-200302834 (1〇) I _say_continued? Z = —— ciT2r where a = 6.2 ± 0.7 is the theoretical value of the aliphatic proton of the main chain And T2r is the D2 value of the expanded sample below the glass transition temperature (Reference: J7ry et al., Mα㈣ (1988) p. 1292). Then the average molecular weight can be determined according to A of Simon et al. / ac / Omo / ecw / a 2_5_ (1992) pages 3624-3628 are calculated as:

Mc = Mu zCoo / n oc c T2 where the molecular weight of the Mu * monomer unit, c 〇 is the number of main chain bonds in the random part, and η is the number of bonds in the main chain. τ2 s considers only those chains that form a reticulated arc (colloid). At the same time, the defect of the network is due to T: 2f. Then from t2s, the effective net arc length of the colloidal part can be measured as: aT2r and the average molar mass of the net 5 melon is:

Mc [克 / 莫尔] = zcjn. 5505 T2s [ms]. According to the invention, the average network arc length of the novel polymer is preferably greater than loooo g / mole, preferably greater than 13000 g / mole, and particularly preferably greater than 140.0 g / mole. It was surprisingly found that the grafting of the rubber and subsequent addition of a hard matrix did not substantially change the I relaxation time described above. Generally, the relaxation time of Ding 2 was reduced by up to 20%, and a relatively short network arc was measured after the grafting of the matrix rubber. Therefore, the T2m relaxation time of the grafted rubber is preferably from 27 to 10 milliseconds, preferably from 2.8 to 10 milliseconds, particularly preferably from 29 to 8 milliseconds. In this novel graft rubber, the net arc length in any case is greater than 10,000 g / mole, preferably 10,300 g / mole, and particularly preferably greater than 105. 〇g / mol. Then ’-15-00 200302834

The relaxation time Th of the grafted rubber is preferably from 24 to 10 milliseconds, preferably from 2 (to 10 milliseconds, particularly preferably from 2.65 to 8 milliseconds. However, the relaxation time distribution of the grafted rubber is more than that of the grafted rubber. Branch rubber is more complicated because, especially with relatively short relaxation times, the occurrence of additional less flowing parts can be attributed to, for example, the rotation of the graft shell.

The characteristic relaxation time of the novel rubber dispersion can be detected even after the graft rubber is added to the hard matrix as an impact modifier. An increase compared to the grafting stage was measured and almost reached the value of the base rubber. The value of Th in this admixture is preferably greater than 3.; t milliseconds, preferably greater than 3 15 milliseconds, and particularly preferably greater than 3.2 milliseconds. The net arc length of the base rubber in the hard matrix is greater than 1 1500 g / mole, preferably greater than 1175 g / mole, and particularly preferably greater than g / mole. The Tk relaxation time is preferably from 27 to 10 milliseconds, and particularly from 28 to 10 milliseconds' and particularly preferably from 2.9 to 10 milliseconds.

The rubber added to the hard base f can be recovered as an insoluble part from the matrix by solvent extraction. After the thermoplastic or thermosetting matrix is removed, the insoluble portion shows a network arc length and relaxation time 'which roughly corresponds to the novel particulate partially or fully crosslinked rubber. The T2s value is then preferably greater than 29 milliseconds, preferably greater than 3.0 milliseconds, and particularly preferably greater than 31 milliseconds. A particulate partially-coupling rubber suitable for use in accordance with the present invention and having the requested network structure, is composed of, for example, the following monomers, the polymer of which has ^ lower than oc: (fluorenyl) propionic acid Ci-Ci8_ Alkyl group, especially (fluorenyl) acrylic acid G-Ct alkyl; siloxanes, such as: dimethylsilyl or diphenylsilane · C2-C32-olefins, diolefins Such as: 丨 Yi Ding Er Chan -16-(12) 200302834

Alkenyl 2fluorenyl β1,3 · pentadiene, hexadiene, phenyl q, 3 · butadiene, 3,4-difluorenyl-1,3 · hexadiene, 1,3-heptadiene, 1,3-octadiene, 4 5-diethylene fl, 3-octadiene, 3-methyl] pentadiene and cardiac methyl], 3.pentadiene. The early body can be copolymerized with other monomers having a Tg higher than 0 ° C, such as: stupid ethylene, (meth) propanol, (meth) acrylic acid and derivatives thereof. The preferred types of rubber are branched copolymers of ethylene olefins (and each other and polyolefins), such as EP & EPDM rubber, copolymers of ethylene and (: 4 to C1 ()-olefins, polybutadiene, Polyisoprene: and its copolymers with styrene, propionitrile, and (meth) acrylates; and polysiloxanes. However, particularly preferred is acrylate rubber, which consists of the following: ai) from 50 Up to 100% by weight of acrylic acid alkyl esters, having a carbon atom, and having only one c = c bond, and as) at least from 0 to 50% by weight of copolymerizable with the heart) Another monomer. The novel rubber is advantageously composed of components from 80 to 99% by weight, preferably from 90 to 99.8% by weight, and from 0 to 20% by weight. /. It is preferably composed of 0.2 to 10% by weight.

The component is particularly preferably selected from n-butyl acrylate and 2-ethylhexyl acrylate. Component & 2) preferably contains from 0.1 to 10% by weight of a cross-linking agent, based on what is called) + & 2). For example, the cross-linking agent may have at least two double bonds, and the double bonds preferably have different reactivity. The preferred cross-linking agents are dihydrodicyclopentadiene acrylate (DCPA, reference: German patent DP1260135) and allyl (meth) acrylate. In the case of acrylate, the graft shell is preferably It consists of styrene, propionitrile, (fluorenyl) acrylic acid vinegar, or preferably a mixture of two or three of these monomers. -17-(13) 200302834

Acrylic dispersion can be prepared by all known polymerization methods from Ip 7A, such as: in solution, in dispersion, in suspension neutron τ as micro-suspension, emulsion, mini-emulsion, etc. It can use free radical, ion,% ion or coordination polymerization method. Preferably, the methods used are those that have resulted in particulate polymers, such as emulsification, mini-emulsification, suspension, and micro-suspension methods. It's a perfect combination. The resulting polymer dispersion then typically has a solids content of from 5 to 80% by volume ', preferably from 10 to 75% by volume', particularly preferably from 15 to 70% by volume. The intermediate particle diameter is from 25 nm to ❻m ', preferably from 50 nm to ⑽m, particularly preferably from 50 nm to 10 m. Common monomers copolymerizable with ai) include: dilute, preferably succinic; (meth) acrylic acid derivatives with alcohol groups up to 32 carbon atoms, (meth) acrylic acid Anhydroglyceride and (fluorenyl) allylamine, butadiene, isoprene, styrene, propionitrile, and cross-linking agents such as: DCPA, and (meth) propylene: dilute propylene is intended to be particularly good The comonomer ^. The granular elastic polymer is prepared in such a manner that the transverse nuclear magnetic resonance relaxation time is within the above range. This polymer can be obtained, for example, by dispersing the component and ad in water, and an emulsifier can be used if necessary. Component a]) contains up to 50% by weight of a cross-linking agent, preferably from 0 ″ to 20% by weight, particularly preferably from 0.2 to 10% by weight, based on ai) and, for example, having at least two Cross-linking agent of a double bond 'The double bond is preferably different in reactivity. The dispersion can then be polymerized with a radical polymerization initiator at from 0 to 150, preferably from 20 to 80 ° C, particularly preferably from 20 to 60. (:. For this purpose and by combining at least two crosslinkers with preferably double bonds of different reactivity, such as: DCPA or allyl (meth) acrylate, obtain -18- (14) (14) 200302834

A network with a considerable mesh arc length, which results in a τ2 relaxation time in the requested range. Because the polymerization proceeds at a relatively low temperature, in fact chain extension occurs better on the more reactive double bonds, while cross-linking occurs less frequently on the less reactive double bonds. The novel polymer can be used as an impact modifier in a grafted or ungrafted form. When used as a graft copolymer, the graft shell preferably consists of those same monomers used to produce a modified hard matrix. Alkyl acrylate rubber is grafted as a graft substrate to modify the styrene / propionitrile copolymer (PS AN based). 'Preferred are styrene / propionitrile (s an), (methyl) Methyl Acrylate (MMA) or SAN-MMA. (There are also p-α-methylstyrene · AN matrix, polybutylene terephthalate (PBT matrix), or a matrix containing polycarbonate (pC), including polyoxymethane (POM), Ethyl chloride (PVC), polyethylene terephthalate (PET), and polyethylene dicarboxylate (pen), or poly (meth) acrylic acid methyl ester (PMMA).) In other words, it is preferable to use acryl vinegar or a reactive group in addition to mmA, such as: weic acid, maleic acid and ISf. In addition to SAN and SAN-MMA, reactive groups are also suitable for modified thermoplastic polyurethane (TPU). Polystyrene (ps) is preferably used as a graft shell to modify the polyphenylene ether matrix (PPE). In order to modify the poly (ether) sulfone matrix, the rubber dispersion may be used in an ungrafted form or a grafted form with s AN. Styrene is preferably used as a graft shell to modify the syndiotactic polystyrene (SPS) matrix. Thermosetting matrices, such as epoxy resins, can be modified with ungrafted or San-grafted rubber dispersions. In order to modify the styrene / polyester thermosetting plastic, the modification is preferably done with an ungrafted or PS-grafted rubber dispersion. -19-200302834 (15) I said that the novel granular elastic polymer can also be used in this compound, such as: ASA / PC, PBT / ASA, PA / ASA, PVC / ASA, ASA / TPU , PPE / PA-ASA, PET / ASA, PEN / ASA, pp-ASA, PE-ASA, PC-P-ester-ASA, and PC-TPU-ASA.

The novel, butadiene acrylic rubber has a net arc length from 115,000 to 50000 g / mole, preferably from 13,000 to 40,000 g / mole, particularly preferably from 14,000 to 3 0.0000 g / mole. At a sample temperature of 14 ° it was found that the lateral relaxation time Th 疋 k ^ .2 to 15 耄 seconds. When measuring the relaxation time distribution, at least 70% of the fast parts were found to have an average lateral relaxation time of 7 ^ from 27 to ιιτι, preferably from 2.8 to 10 ms, especially from 30 to 8 millisecond. The findings based on this invention can also be used for production control and quality control. g This can study samples at any desired stage of production, that is, after the rubber is prepared, after the rubber is grafted, or after the mold material is prepared, and the relaxation time or relaxation time distribution can be monitored . Therefore, the present invention is also related to the quality control of granular partially crosslinked rubber, in which the granular: crosslinked rubber, or a sample of a graft copolymer prepared based on the rubber can be obtained.

Or the mold substance containing the rubber or the graft copolymer, and the birch magnetic field; the loose time distribution h (T2) or h (ton) is measured by the method of nuclear magnetic resonance / The following examples illustrate the present invention. Congratulations on 1 granular elastic polymer Unless otherwise stated, ‘Use the following chemicals · Demineralized water saturated with nitrogen;

Cl2-Cu_ sodium salt emulsifier of paraffin sulfonic acid: in 40% strength aqueous solution (emulsifier K30 from Bayer); -20- 200302834 〇6) n-butyric acid (BA): After distillation in a rotary evaporator; Crosslinker: DCPa; Catalyst: Dissolve E-Fe 13 from Akzonobd (this is 0.1% strength ethylene diamine tetraacetic acid ferric salt (EDta iron in Sodium salt) in water). Styrene and propionol were obtained from BASF AG and used without further purification. Preparation of seed latex: 33 53 g of demineralized water, 55 5 g of emulsifier κ 3 0 in 40% strength aqueous solution. 6.7 g of potassium persulfate and 86 g of NaHC03 were introduced into a round bottom glass flask. The reaction mixture was heated to 6 (rc. 217.6 g of butyl acrylate and 4.4 g of DCPA was quickly added. Another 4 g of butyl acrylate and 39.6 g of DCPA were added in the following three and a half hours The internal reaction time is 2 hours. Therefore, the solid content of the obtained latex is 39.8%. Measurement of the dent impact strength: According to ISO, Izod having a size of 4 mm x 7 mm x 79.2 mm is used. Test species to measure the dent impact strength. For this purpose, the graft copolymers prepared in Examples 1 and 2 and Comparative Examples 3 and 4 were added with a copolymer composed of 67% by weight of styrene and 33% by weight of propionitrile. In the matrix, a 0.5% strength copolymer solution in dimethylformamide with a viscosity of 80 ml / g (measured at 23.0; DIN 53726). For this purpose, 417% by weight of the graft copolymer In 58.3% by weight of the copolymer, it was mixed in an extruder (ZSK 30, Warner & Pfleiderer), and heated in a prayer mold heated to 50 ° C at 27 ° C. (Extruded at TC. The mold material has a large melt volume index In • 21-(17) (17) 200302834 30 liters / 10 knives 4 miles (according to Ø S0 u 33 B, at 22〇 ... measured using fine particles of the mold material and load 2.16 kg). Measurement of relaxation time distribution (Measured by NMr). The dispersion was poured into a layer with a thickness of about 1 mm, and the water content of the dispersion was evaporated in 23.0 air and extraction clearance for 12 hours, and in an evacuation oven under reduced pressure for 3 hours. About 5,000 g of the dry substrate stage and the grafting stage were introduced into the celebrity officer (filled 10 degrees south), and the blank volume was flushed with gas and nitrogen.

2 and the measuring tube is closed with fusion. Ding 2 was measured at a sample temperature of 14 ° C and was ordered by NMR analysis (from Bruke model. For Ding 2: the amount and evaluation method are known to those skilled in the art. In this example, the method described in detail in the field is described in Andrew's (And Rus) et al's 4 corpses from 69 989 years, page 89. For the relaxation time distribution of the non-sol-soluble part of the mold material, It was measured that 10 g of a tungsten mold substance was added to 16 () liters of methyl ethyl ether at 2 rc, and allowed to stand for 24 hours. Then, centrifugation was performed at 14,000 rpm for 15 hours Then, continue decantation. This step is repeated twice more. Then the obtained insolubilized σ | M knife is dried under reduced pressure of 60 ° C and 1 mHg for 16 hours. Then the relaxation time distribution is measured. Example 1 For the preparation of the rubber substrate, 1 3 0 g of demineralized water, 2 37 g of emulsified d K 30 (40% strength aqueous solution) (1%, based on monomers), 92.9 g of Acrylic acid and 19.0 grams of DCPA were introduced into a glass reactor and heated to 40% under nitrogen. Between, i 2 billion billion grams of water and 5.7 g of potassium persulfate was added to the reaction mixture, which temperature is maintained at -22--200302834

(18) The subsequent reaction time at 40 C ° is 9 hours. A sample of the dispersion thus obtained was sampled and analyzed. The sample had a solids content of 38 2%. The D2 relaxation time distribution and net arc length of the rubber are summarized in Table 丨 (rows 丨 0). For the preparation in the grafting stage, 2195.0 grams of water were first added and the reaction mixture was heated to 60 ° C. After adding 2.4 g of potassium persulfate, 4 57.3 g of styrene and 152.4 g of propionitrile were allowed to proceed for a period of 130 minutes. Polymerization was completed at 60 ° C for another 2 hours. After the reaction was completed, samples from the grafting stage were sampled and analyzed (Table 1: 1P). The sample had a solids content of 29.5%. The intermediate particle size was 170 nm. The aforementioned mold materials were prepared and analyzed in a corresponding manner (Table 1: 1B). The depression impact strength (measured at 23 t) of the mold substance was 5 丨 5 kJ / m 2. The non-solubilized part was then extracted from the mold material described above and analyzed similarly (Table 1: 1U). Example 2 1055.0 grams of demineralized water was initially placed in a glass reactor. 12.7 grams of seed latex, 3.8 grams of NaHC03 and 4.0 grams of Disolvine solution were added, and the mixture was heated to 40 under nitrogen. (: The following is allowed for 5 hours: 1) 1000 g of butyl acrylate and 20.4 g of DCPA; 2) 243.0 g of demineralized water, 4.5 g of ascorbic acid and 15.3 g of a 40% strength K30 solution; 2) 243.0 grams of demineralized water and 15.0 grams of a 30% strength hydrogen peroxide solution in water. The polymerization was completed with stirring for another 100 minutes. The base material stage thus obtained 200302834

The solid content of paragraph (19) was 38.7% (the measurement results are in Table i: 2G). For the preparation in the grafting stage, 1578.9 grams of demineralized water and 4.7 grams of a 40% strength K3 0 solution were added to the dispersion, and the mixture was then heated to 60 ° C. This was continued with the addition of 1.8 g of potassium persulfate. 221 grams of styrene were added over a period of 60 minutes. After a subsequent reaction of 60 minutes, a mixture of 344.3 g of styrene and 1 1 4.7 g of propionitrile was allowed to proceed for a period of 2 hours. Post-polymerization was then completed in 3 hours. Therefore, the solid content of this grafting stage was 34. 1%, and the intermediate particle size was 150 nm (the analysis results are shown in Table 1: 2P). The mold substance and the insoluble portion of the mold substance were prepared and analyzed as in Example 1 (the results are shown in Tables 1: 2 B and 2 U). The depression impact strength (measured at 2 3 ° C) of this mold substance was thus 4 9.3 kilojoules per square meter. Example 3 (Comparative) 4140.4 grams of demineralized water and 51.9 grams of seed latex were initially placed in a glass reactor and heated to 65 ° C under nitrogen. 9.3 g of potassium persulfate and 11.9 g of NaHC03 were added. The following mixtures were permitted in the reactor: 1) 3031.0 g of butyl acrylate and 61.9 g of DC PA; 2) 5 18.0 g of water and 46.3 g of a 40% strength K30 solution. 10% of the mixture 1) was added over a period of 20 seconds, and the remainder was added over a period of $ hours. Mixture 2) was allowed to proceed over a period of 5.5 hours. The anti-humanity temperature was kept at 65 ° C. After that, additional polymerization was completed in 35 minutes, and a sample of the rubber substrate stage thus obtained was taken. The solids content of this sample was 39.2% (Table 1: 3G). 200302834

(20) For the preparation in the grafting stage, the dispersion in the substrate stage is filtered (sieve size: 500 microns). 3765 grams of dispersion, 1467 grams of water, and 128 grams of emulsifier K3 0 (40% strength aqueous solution) were introduced into a round bottom glass flask and heated to 65 ° C. Then 3.9 g of potassium persulfate was added. The dispersion was grafted in a two-stage process. 3206 grams of styrene were added over a period of 90 minutes. This was followed by a follow-up reaction of 1 hour. Then 4 " · 4 grams of styrene and 克 α. 5 grams of the propionitrile mixture was added over a period of 90 minutes. The mixture was allowed to undergo repolymerization for 2 hours. The solids content of the obtained grafting stage was therefore 39%. The intermediate particle size is 580 nm. The results are summarized in Table 1 (3p). The mold substance and the insoluble portion of the mold substance were analyzed according to Example 1 (3 b and 3 U). The dent impact strength (measured at 23 ° C) of the prepared mold material was therefore only 13.2 kJ / m². Example 4 (comparative example) 2966 grams of demineralized water and 28.5 grams of seed latex were initially placed in a round bottom glass flask and heated to 60 ° C under nitrogen. Then 6.6 g of potassium persulfate and 8.5 g of NaHC03 were added. A mixture of 2165 grams of butyl acrylate and 44.2 grams of DCPA was allowed to take place over a period of 3.5 hours, and a mixture of 370 grams of water and 33.1 grams of K 3 0; the grain solution was carried out over a period of 4 hours. The post-polymerization time was 2 hours. The base rubber thus obtained had a solids content of 38.9% (Table 1: 40). For grafting the rubber ' 2229 grams of demineralized water, 19.3 grams of a [30 solution and 5.9 grams of potassium persulfate were added to the substrate stage at 60 ° C. 4 8 1 gram of styrene is allowed to take place over a period of 1 hour. After that, the polymerization time was 1 hour. After that, a mixture of 749 g of styrene and 250 g of propionitrile was allowed to carry out for 2 hours -25-200302834 (21) I _say_ Continued: time, and then the reaction mixture was polymerized for 2 hours. This grafting stage therefore has a solids content of 39.1% and an intermediate particle size of 500 nm (test results are in Table 1: 4P). The mold substance and the insoluble portion of the extracted mold substance were analyzed according to Example 1 (Table 1: 4B and 4U). The depression impact strength (measured at 23 ° C) of the obtained mold material was therefore only 18.5 kJ / m². τ2 T2s Ps T2f Pf Mesh arc length (140 ° milliseconds milliseconds milliseconds% g / mole instance 1 1G 4.15 3.85 90 35 10 16427 1P 3.27 3.05 94 20 6 13013 1B 3.83 3.65 98 10.5 2 15573 1U 3.80 3.63 96 10.7 < 5 15488 Example 2 2G 4.17 3.49 79 20 21 14891 2P 3.22 2.84 89 10.5 11 12117 2B 3.62 3.26 87 9 13 13909 2U 3.83 3.44 90--14677 Example 3 (Comparative) 3G 2.88 2.16 77 8 23 9216 3P 2.38 1.87 78 6.5 22 7979 3B 2.66 2.10 79 6.5 21 9003 3U 2.57 2.19 84 Painting-9344 Example 4 (Comparative) 4G 3.15 2.62 81 9 19 11179 4P 2.67 2.33 90 10.3 10 9941 4B 3.02 2.65 90 9 10 11307 4U 3.34 2.83 90- -12075

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Claims (1)

200302834 Patent application scope 1. Kind of granular part $ wearing & Six Lectures * 全 a / full ^ rubber, with glass transition temperature lower than 0 ', the rubber has a network of dots connected to each other by a network of foxes, Reticulated foxes have an average molecular weight from 10,000 to 5000 g / mole. 2: The rubber according to item 1 of the patent range, wherein the average molecular weight of the reticulated fox is from 13,000 to 40,000 g / mole, preferably from to 2,000 g / mole. 3.-A kind of granular partially crosslinked rubber 'has a glass transition temperature lower than that of acrylene, and the relaxation of the transverse magnetization of the rubber nucleus is based on the transverse relaxation time (U description, when measured at 140t, it is from 3 15 milliseconds. 4. As for the rubber in the third item of the patent application scope, the looseness of the transverse magnetization is described by at least a double statistical (bmiodal) relaxation time distribution (h (T2)), and the first mouth is at least 70. % Has an average lateral relaxation time (T2s) from 2 to ^ milliseconds, preferably from 2.8 to 10 milliseconds, particularly preferably from 30 to 8 milliseconds. 5. If the patent application S No. 4 rubber, the second part The proportion is not more than 30%, and the average lateral relaxation time (T ^) is greater than 10 milliseconds. 6 'As claimed " Any of the items in the patent range 3 to 5 rubber, wherein the polymer There are reticulated foxes whose average molecular weight is greater than 0 g / mole, preferably greater than 13 g / mole, and particularly preferably greater than 14,000 g / mole. 7. The range of patents from Shenqing No. 丨 to 6 The rubber of any one of clauses, which is composed of the following: Heart) 50 to 100% by weight of at least one alkyl acrylate Base ester, an alkyl group having 1 to 6 carbon atoms and only one c = c bond; and 2) at least another monomer copolymerizable from 0 to 50% by weight. 8. If the rubber in the scope of patent application No. 7 is applied, it is from 2003 to 998% by weight. Component ai), preferably from 90 to 998% by weight, and component 0 "to 20% by weight, component ad, preferably from 0.2 to 10% by weight. /. Composed of. 9. The rubber according to any one of claims 7 and 8 in the declared patent scope, wherein the component is selected from the group consisting of n-butyl acrylate and 2-ethylhexyl acrylate. 10. If the rubber according to any one of claims 7 to 9, the component a2) contains a crosslinking agent from 0.1 to 10% by weight, based on a 1) +). 11. A method for preparing a rubber according to any one of items 7 to 10 of the scope of the patent application, which comprises: from 50 to 100% by weight of an alkyl acrylate, a alkynyl group having ^ 30 carbon atoms, And there is only one C = c bond, and at least another monomer copolymerizable with ai) from 0 to 50% by weight, containing at least 0 to 10% by weight of a crosslinking agent, based on ai) + a2) It is polymerized. If an interfacial active composition is needed, there is a radical polymerization initiator to polymerize from 30 to 50 ° C, preferably from 35 to 45. (:, Especially good about 40 ... Hanru's method of applying for the scope of the patent item 丨 丨, in which the cross-linking agent used is DCPA or (fluorenyl) dipropyl propyl methacrylate. 13. ·丨 丨 and the method of any one of 12, wherein the component is selected from the group consisting of n-butyl acrylate and 2-ethylhexyl acrylate. 14. A graft copolymer comprising The grafted substrate is prepared by grafting, preferably from 5 to 95% by weight, and particularly preferably from 10 to 90% by weight. The substrate is any one of items 7 to 10 of the scope of patent application. The rubber according to item 'The rubber has a grafted shell from 0.1 to 99.9% by weight, preferably from 5 to 95% reset', and is particularly preferably from 10 to 90% by weight. 200302834 15. In the case of a graft copolymer according to item 14 of the patent application, the graft shell comprises styrene-acrylic acid, an ester of (meth) acrylic acid, or a mixture of these monomers. 16. Use of a rubber as claimed in any of claims} to 10 or a graft copolymer as claimed in any of claims 14 and 15 to increase the dent impact of a thermoplastic or thermosetting mold substance strength. Π · —a thermoplastic or thermosetting mold substance, comprising from 1 to 99 parts by weight of a thermoplastic or thermosetting polymer as a matrix, preferably from 5 to 95 parts by weight, particularly preferably from 10 to 90. Parts by weight; from UN parts by weight " the aberration of any of the patent scope items 7 to 10, and / or the patent application of the graft copolymer = any of the graft copolymers of any of 14 and 15, compared with It is preferably from 5 to% parts by weight. 'Extremely good is from 1 () to 9 () parts by weight, and conventional additives up to parts by weight, the insoluble portion separated from the mold substance, when When measured at 14 ^ C, it has a lateral relaxation time (T2m) from 3 to 10 milliseconds. 18 · If you apply for a patent || Every change of material of the 17 members of Zhu Chu, where the transverse magnetism and relaxation of the rubber win can be described by the double statistical relaxation time distribution h (T2), the hair I '4 inch is best from 30 to 8 milliseconds. 19. A molded article containing Shen Bianhuang 4: Patent ... any of the 17- and 18-item prayer materials 20. 20. A granular part The rubber or spoon. Mouth control method, in which ^ one m rubber or graft copolymer is obtained as the base material, the granular part of the cross-linked rubber or, the γ, the magnetic distribution of the loose time distribution is a square: a " The sample is measured by nuclear magnetic resonance method. 200302834 Lu, (a), the representative representative of this case is shown in the figure; (b), the representative symbol of the element in this case is simply explained: 柒, if there is a chemical formula in this case, Please reveal the chemical formula that best characterizes the invention: