JPS62259818A - Mafnufacture of molded body of polyacrylic metal salt - Google Patents
Mafnufacture of molded body of polyacrylic metal saltInfo
- Publication number
- JPS62259818A JPS62259818A JP26935585A JP26935585A JPS62259818A JP S62259818 A JPS62259818 A JP S62259818A JP 26935585 A JP26935585 A JP 26935585A JP 26935585 A JP26935585 A JP 26935585A JP S62259818 A JPS62259818 A JP S62259818A
- Authority
- JP
- Japan
- Prior art keywords
- metal salt
- polyacrylic acid
- polyacrylic
- metal
- molded body
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 42
- 239000002184 metal Substances 0.000 title claims abstract description 42
- 150000003839 salts Chemical class 0.000 title claims abstract description 31
- 238000002844 melting Methods 0.000 claims abstract description 3
- 230000008018 melting Effects 0.000 claims abstract description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 41
- 239000004584 polyacrylic acid Substances 0.000 claims description 41
- 239000000843 powder Substances 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 238000000465 moulding Methods 0.000 claims description 10
- 238000011049 filling Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 7
- 230000006835 compression Effects 0.000 abstract description 3
- 238000007906 compression Methods 0.000 abstract description 3
- 239000007789 gas Substances 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001873 dinitrogen Inorganic materials 0.000 abstract description 2
- 239000001307 helium Substances 0.000 abstract description 2
- 229910052734 helium Inorganic materials 0.000 abstract description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 229910044991 metal oxide Inorganic materials 0.000 description 7
- 150000004706 metal oxides Chemical class 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 229920000058 polyacrylate Polymers 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- -1 *Zn Chemical class 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910010068 TiCl2 Inorganic materials 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明のポリアクリル酸金属塩の成型体は、高い耐熱性
と圧縮弾性率を有し、歯車、ギヤー、航空機材、建築構
造材料、ｄ子・ポス材料として有用である。Detailed Description of the Invention [Industrial Application Field] The molded product of the metal polyacrylate of the present invention has high heat resistance and compressive modulus, and is suitable for use in gears, gears, aircraft materials, building structural materials, d It is useful as a child/post material.
ポリアクリル酸ソーダの成形方法としては、これを水性
溶媒に溶解し、これをキャスティングしてフィルムを製
造する方法が如られている〔エル、イー、ニールセン部
署”ブロン−ティング ロイヤルソサエテイ“、２８２
Ａ、１３７頁、１９６４年刊（Ｌ、Ｅ、 Ｎ１ｅｌｓｅ
ｎ ｅｔ、 ａｌ、 ： Ｐｒｏｃｅｅｄｉｎｇ Ｒｏ
ｙａｌＳｏｃｉｅｔｙ ）。A method for molding sodium polyacrylate is to dissolve it in an aqueous solvent and cast it to produce a film [Bronting Royal Society, L.E., Nielsen Department, 282].
A, 137 pages, published in 1964 (L, E, N1else
net, al, : Proceeding Ro
yalSociety).
また、ポリアクリル酸粉末と二圃金属酸化・物の混合粉
末を金型内に充填し、この金型をポリアクリル酸の融点
以上；（加熱してポリアクリル酸を溶融させて金属酸化
□吻と反応させて；ｉ＜ ｌ）アクリル戚金属塩を生成
させ、これを加圧成形する方法も知られている〔アール
舎ニス・スティ著１イオンコンテイング ボリマーズ、
１９７７年刊（Ｒ。In addition, a mixed powder of polyacrylic acid powder and two metal oxides/products is filled into a mold, and the mold is heated to melt the polyacrylic acid and form a metal oxide. A method is also known in which an acrylic metal salt is produced by reacting with i < l) and then pressure molded [1 Ion Containing Polymers by Nis Suti, R.S.A.
Published in 1977 (R.
Ｓ、 ５ｔｅｉ ； Ｉｏｎ−Ｃｏｎｔａｉｎｉｎｇ
Ｐｏｌｙｍｅｒｓ ）。S, 5tei; Ion-Containing
Polymers).
前記キャスティング方法で得られるフィルムは非常に脆
く、割れや亀裂も多く実用的でない。The film obtained by the above casting method is very brittle and has many cracks and cracks, making it impractical.
後者の金型内で溶融ポリアクリル酸と二価金属酸化物と
を反応させる方法では、ポリアクリル酸と金属酸化物を
均一に混合することができなく、また、ポリアクリル酸
と金属酸化物との反応も理論量適りには行われず、未反
応の金属酸化物が充填剤として成型体に残存し、これら
が原因となって、得られる成型体には巣や不均一部分が
残り、成型体Ｆｉ別れや亀裂が生じやすいものである。In the latter method, in which molten polyacrylic acid and divalent metal oxide are reacted in a mold, polyacrylic acid and metal oxide cannot be mixed uniformly, and polyacrylic acid and metal oxide cannot be mixed uniformly. The reaction also does not take place in the stoichiometric amount, and unreacted metal oxides remain in the molded product as a filler, which causes cavities and non-uniform areas to remain in the resulting molded product, resulting in poor molding. Body Fi separation and cracks are likely to occur.
更に後者の方法では成型体の離型性が悪い。Furthermore, in the latter method, the releasability of the molded product is poor.
また従来技術では、ポリアクリル酸と３価金属および４
価金属との塩の成形物は帰られていない。In addition, in the conventional technology, polyacrylic acid, trivalent metal and quaternary
Salt moldings with valuable metals have not been returned.
本発明においては、加圧成形する樹脂素材として熱不融
性であるポリアクリル酸の４価の金属塩を用いることに
より、雌型性が良好で、圧縮弾性率が１５〜４０ギガパ
スカル（ＧＰａ）、！：高い弾性率を有する成形体を得
ることができる。In the present invention, by using a heat-infusible tetravalent metal salt of polyacrylic acid as the resin material to be pressure molded, it has good female moldability and a compressive elastic modulus of 15 to 40 gigapascals (GPa ),! : A molded article having a high elastic modulus can be obtained.
即ち、本発明は、ポリアクリル酸金属塩を構成する金属
が、４価の金属が１０〜１００モル％で、１価および／
または２価および／または３価の金属が９０〜θモル％
であるポリアクリル酸金属塩の粉末を型内に充填後、１
ｏｏｕ／−＋＋ｆ以上１００万蛇／−以下の圧力でかつ
、該ポリアクリル酸金属塩の融点より低い温度条件で加
圧成形して成形体とすることを特徴とするポリアクリル
酸金属塩の成形体の製造方法を提供するものである。That is, in the present invention, the metal constituting the polyacrylic acid metal salt contains 10 to 100 mol% of tetravalent metal, monovalent metal and/or
or 90 to θ mol% of divalent and/or trivalent metals
After filling the mold with polyacrylic acid metal salt powder, 1
Molding of a polyacrylic acid metal salt, characterized in that it is pressure-molded into a molded body at a pressure of oou/-++f or more and 1,000,000 kah/- or less and at a temperature lower than the melting point of the polyacrylic acid metal salt. The present invention provides a method for manufacturing a body.
（ポリアクリル酸金属塩）
４価金属を含有するポリアクリル酸金属塩は、例えばポ
リアクリル酸と、４価の無機金属塩または４価の無機金
属塩と他の無機金属塩の混合物とを、ポリアクリル酸の
カルボキシル基（−ＣＯＯＨ）１当量に対し、金属イオ
ンが０．１〜２０当量の割合となるように、アルカリ金
属水酸化物の水溶液中で反応させて沈澱として析出させ
ることにより得られる。(Polyacrylic acid metal salt) A polyacrylic acid metal salt containing a tetravalent metal is, for example, a mixture of polyacrylic acid and a tetravalent inorganic metal salt or a tetravalent inorganic metal salt and another inorganic metal salt, Obtained by reacting in an aqueous solution of an alkali metal hydroxide and depositing it as a precipitate so that the metal ion is in a ratio of 0.1 to 20 equivalents per equivalent of carboxyl group (-COOH) of polyacrylic acid. It will be done.
４価の金属イオンとしてはＴｉ”、Ｓｎ４″″、ｚｒ４
“、Ｔｅ 、 Ｐｂ 、 Ｍｒ３． Ｒｕ 、
Ｒｅ 等が利用できる。これらは２種以上混合
して用いてもよい。Ti'', Sn4'''', zr4 as tetravalent metal ions
", Te, Pb, Mr3. Ru,
Re etc. can be used. Two or more of these may be used in combination.
他の価の金属イオンとしてはＬａ３＋、ＡＬ３“、Ｆｅ
”等の３価イオン＊Ｚｎ ＸＭｇ 、 Ｃａ 、
Ｂａ 。Other valent metal ions include La3+, AL3", Fe
Trivalent ions such as *Zn, XMg, Ca,
Ba.
Ｓｎ２＋、Ｆｅ”、 ｐｂ２＋、Ｃｕ２４−等の２価
イオン：Ｎａ”、Ｋ”、Ｌｉ”、Ｃｕ＋、んＣ等の１価
イオンが利用できる。これらも混合して用いることがで
きる。Divalent ions such as Sn2+, Fe", pb2+, Cu24-, etc.; monovalent ions such as Na", K", Li", Cu+, and C can be used. These can also be used in combination.
ポリアクリル酸は、アクリル７４３８０〜１００モル％
ト、他のビニルモノマー２０−０モル％トヲ重合もしく
′は共重合させることにより得られる。Polyacrylic acid is acrylic 74380-100 mol%
(20-0 mol %) of other vinyl monomers or copolymerization.
このポリアクリル酸の重合度は、５０〜１，０００゜０
００であり、成形体を高強度にするためには重合度が大
きい方が良いので１００以上が好ましく、ポリアクリル
酸金属塩の製造時に使用するポリアクリル酸水ａ？？Ｉ
は重合度が小さい方が粘）ｌが小さく取扱いが容易なの
で１００．０００以下が好ましい。The degree of polymerization of this polyacrylic acid is 50 to 1,000°0.
The degree of polymerization is preferably 100 or more because it is better to have a higher degree of polymerization in order to make the molded product high in strength, and the polyacrylic acid water a? ? I
The smaller the degree of polymerization, the smaller the viscosity (l) and the easier handling, so it is preferably 100,000 or less.
反応により析出沈澱したポリアクリル酸金属塩は、濾過
により水性溶媒と分離させた後、水洗を操り返し、水溶
性のポリアクリル酸と、未反応の無機塩、副生じた無機
塩を水に溶屏させてポリアクリル酸金属塩粉末より除去
し、ついでポリアクリル酸金属塩粉末を乾燥させ、必要
により粉砕し、ｏ、ｏ ｉ〜ＳＯＯミクロンの粉末とし
、成形材料とする。緻密な成形体を得るには粒径は小さ
い方が良いので２００ミクロン以下が好ましく、取扱い
の面では粒径は大きい方が容易なのでｏ、ｔ ミクロン
以上が好ましい。The polyacrylic acid metal salt precipitated by the reaction is separated from the aqueous solvent by filtration, and the water washing is repeated to dissolve the water-soluble polyacrylic acid, unreacted inorganic salts, and by-product inorganic salts in water. The polyacrylic acid metal salt powder is separated and removed from the polyacrylic acid metal salt powder, and then the polyacrylic acid metal salt powder is dried and, if necessary, crushed to obtain a powder of o, o i to SOO microns, which is used as a molding material. In order to obtain a dense molded body, the smaller the particle size, the better, so the particle size is preferably 200 microns or less, and from the viewpoint of handling, the larger the particle size, the easier it is, so the particle size is preferably o,t microns or more.
ポリアクリル酸金属塩は、不融性で、１〜１０ｏ、ｏ
ｏ ｏ気圧下では５００℃以下の温度では溶融しない。The polyacrylic acid metal salt is infusible and has a molecular weight of 1 to 10 o, o
o It does not melt at temperatures below 500°C under atmospheric pressure.
（成型体の製造）
成型体は、ポリアクリル酸粉末を第１図に示す圧縮金型
のキャビティ（１１内に充填し、これを５０〜５００℃
、好ましくは、成形を促進するためにｉｏｏ℃以上、ポ
リアクリル酸成分の分解を防ぐために４００℃以下で、
１００〜１，０００，０００ｋＶ／ｄ、好ましくは緻密
な成形体を得るために１，０００ 搾／ｃｄ以上、容易
に入手でき繰返し使える型の耐圧性能の面からは１００
，０００ ｋＷ／ｃｎｉ以下の圧力下で行なう。図中、
１はキャビティ、２はキャビティ形成用ハウジング材、
３はピストン棒、４は７リンダー、５はＯ−リング、６
ば〇−リング抑え、７は外筒、８は外筒上部、９は外筒
下部、１０は排気管である。(Manufacture of molded body) To produce the molded body, polyacrylic acid powder is filled into the cavity (11) of a compression mold shown in FIG.
, preferably above 100°C to promote molding and below 400°C to prevent decomposition of the polyacrylic acid component.
100 to 1,000,000 kV/d, preferably 1,000 compression/cd or more in order to obtain a dense molded body, and 100 kV/cd or more in terms of pressure resistance of a mold that is easily available and can be used repeatedly.
,000 kW/cni or less. In the figure,
1 is a cavity, 2 is a housing material for forming the cavity,
3 is the piston rod, 4 is the 7 cylinder, 5 is the O-ring, 6
7 is an outer cylinder, 8 is an upper part of the outer cylinder, 9 is a lower part of the outer cylinder, and 10 is an exhaust pipe.
加圧成形時の雰囲気は、窒素ガス下、ヘリウムガス下、
空気下等何であってもよい。加圧成形は、威圧下（０，
０００１〜ｔｏｏｍＨｇ）に行うのが好ましい。The atmosphere during pressure molding is under nitrogen gas, helium gas,
It may be under air or anything else. Pressure molding is performed under pressure (0,
0001~toomHg).
成唄木の形状は棒状、板状、歯車状等任意である。この
成型体は、必要に応じて熱処理を行ったり、切削や切断
加工、穿孔加工等が可能である。The shape of the tree can be arbitrary, such as a rod, a plate, or a gear. This molded body can be subjected to heat treatment, cutting, cutting, perforation, etc., as necessary.
（発明の効果） 本発明の効果を箇条書すれば次の通りである。(Effect of the invention) The effects of the present invention can be summarized as follows.
（１） フィルム状に限らず、棒状、板状、ブロック
状、カム、歯車等任意の形状の成型体が得られる。(1) It is possible to obtain a molded body not only in the form of a film but also in any shape such as a rod, a plate, a block, a cam, a gear, etc.
（２）成型体は高い曲げ弾性率（例えば３ギガパス力ル
以上）、耐熱性を有し、割れや亀裂がない。(2) The molded product has a high flexural modulus (for example, 3 gigapath force or more), heat resistance, and is free from cracks and cracks.
以下、実施例により本発明を更に詳細に説明する。Hereinafter, the present invention will be explained in more detail with reference to Examples.
ポリアクリル酸金属塩の製造例：
製造例１
重合度ｓ、ｏ ｏ ｏのポリアクリル酸０．１当量が溶
解している水ｆ＠液５００ω中に、ＴｉＣｔ４０−１当
１が溶解している水／エタノール（９／１ ）混合溶液
３００ＣＣを攪拌しつつ滴下した後、更にＮａ ＯＨＯ
，１当量が溶解している水溶、１２００ＣＣを攪拌しつ
つ滴下させた。Production example of polyacrylic acid metal salt: Production example 1 1 equivalent of TiCt40-1 is dissolved in water f@liquid 500Ω in which 0.1 equivalent of polyacrylic acid with a degree of polymerization s and o o o is dissolved. After dropping 300 cc of water/ethanol (9/1) mixed solution with stirring, further Na OHO
An aqueous solution containing 1 equivalent of 1,200 CC was added dropwise with stirring.
生じた沈澱を濾過と水洗とを繰り返した後に乾燥し、粉
砕することにより、当量比１吋１のポリアクリル酸チタ
ンの粉末を得た（粉末Ｉ）。The resulting precipitate was repeatedly filtered and washed with water, then dried and pulverized to obtain titanium polyacrylate powder with an equivalent ratio of 1:1 (Powder I).
製造例２
重合度５，０００のポリアクリル１唆０．１当量が溶解
している水＠１５００匡中に、Ｔｉα４０．２当量が溶
解している水／エタノール（９／１ ）混合溶液３００
ｃＣを攪拌しつつ滴下した後に、Ｎａ０ＨＯ０２当−量
が溶解している水溶液２００ＣＣを攪拌しつつ滴下させ
た。Production Example 2 A mixed solution of water/ethanol (9/1) in which 40.2 equivalents of Tiα is dissolved in 300 m2 of water in which 1 to 0.1 equivalent of polyacrylic having a degree of polymerization of 5,000 is dissolved.
After cC was added dropwise with stirring, 200 CC of an aqueous solution containing 2 equivalents of Na0HO02 was added dropwise with stirring.
生じた沈澱を濾過と水洗とを操り返した後に乾燥し、粉
砕することにより、当量比１対２のゴζリアクリル酸チ
タンの粉末を得た（粉末■）。The resulting precipitate was repeatedly filtered and washed with water, then dried and pulverized to obtain a powder of titanium ζ-lyacrylate having an equivalent ratio of 1:2 (powder ■).
製造列３
重合ｆ ５，０００のポリアクリル酸０．１当量が溶解
して１ハる水溶１５００ｃｃ中に、ＴｉＣｔ４０．４当
量が溶解している水／エタノール（、９／１ ）混合溶
液３００ＣＣを攪拌しつつ滴下した後に、Ｎａ０ＨＯ１
４当量が＠５−シている水溶液２００ｃｒ−を攪拌しつ
つ滴下させた。Production row 3 Polymerization 300 cc of a water/ethanol (9/1) mixed solution in which 40.4 equivalents of TiCt are dissolved is added to 1500 cc of an aqueous solution containing 0.1 equivalent of polyacrylic acid having a polymerization f of 5,000. After dropping with stirring, Na0HO1
200 cr of an aqueous solution containing 4 equivalents of @5 was added dropwise with stirring.
生じた沈澱を濾過と水洗とを操り返した陵に乾罎し、粉
砕することにより、当量比１対４のポリアクリル酸チタ
ンの粉末を得た（粉末■）。The resulting precipitate was filtered and washed with water, dried, and pulverized to obtain titanium polyacrylate powder with an equivalent ratio of 1:4 (powder ■).
製造例４
重合ｉ５，０００のポリアクリル酸０．１当量が溶解し
て□ハる水溶液５００ＣＣ中に、Ｓｎつ４０．１当Ｉ介
が１’４？ｆｊしてハる水／エタノール（９／１）混合
溶液３００ｃ１１１．を攪拌しつつ滴下した後に、Ｎａ
０ＨＯ０１当量が溶解している水５Ｐ２Ｌ２ｏｏｃｃを
撹拌しつつ滴下させた。Production Example 4 Polymerization 0.1 equivalent of polyacrylic acid with i5,000 is dissolved in 500 cc of an aqueous solution, and 40.1 equivalents of Sn are dissolved in 1'4? fj water/ethanol (9/1) mixed solution 300c111. After dropping Na while stirring,
5P2L2oocc of water in which 0HO01 equivalent was dissolved was added dropwise with stirring.
生じた沈澱をテ過と水洗とを操り返した後に乾燥し、粉
砕することにより、当量比１対工のポリアクリル酸スズ
の粉末を得た（粉末１’ｌ／）、、。The resulting precipitate was repeatedly filtered through a filter and washed with water, then dried and pulverized to obtain a powder of tin polyacrylate with an equivalent ratio of 1:1 (powder 1'l/).
製造例５
重合ｆｉ５，０００のポリアクリル酸０．１当量が溶解
している水Ｍ孜５ｏｏｃｃ中に、５ｎＣＬｔ ０．２
’Ｉ ＱＨが溶解している水／エタノール＜、 ９／１
）Ｔ見合、５夜３００ＣＣを攪拌しつつ滴下した後に
、ＮａＯＨ０，２当扉：が溶解している水ｌ＠液２００
ＣＬを攪拌しつつ滴下させた。Production Example 5 In 50cc of water in which 0.1 equivalent of polyacrylic acid with a polymerization fi of 5,000 is dissolved, 5nCLt 0.2
'Water/ethanol in which I QH is dissolved<, 9/1
) After dropping 300cc with stirring for 5 nights, add 200 liters of water in which NaOH0,2 is dissolved.
CL was added dropwise while stirring.
生じた沈澱を濾過と水洗とを、柔り返した麦に乾燥し、
粉砕することにより、当量比１対２の（ミリアクリル酸
スズの粉末を邊た（粉末■）。The resulting precipitate is filtered and washed with water, then dried into softened wheat.
By grinding, tin miliacrylate powder was prepared in an equivalent ratio of 1:2 (powder ■).
製造例６
重合度５，０００のポリアクリル、波０．１当虫が溶解
している水＋Ｂａ５ｏｏｃｃ中１Ｃ１３ｎ（Ｊ４０−４
当寸がｒ容４している水／エタノール（９／１）・見合
り、−；？２ｉ、３００ＣＣを攪拌しクク滴下した後に
、Ｎａ０ＨＯ１４当量が溶解している水溶液２００ＣＣ
を撹拌しつつ滴下させた。Production Example 6 Polyacrylic with a degree of polymerization of 5,000, 1C13n (J40-4
Water/ethanol (9/1) with an actual size of r volume 4, matching, -;? After stirring and dropping 2i, 300CC, 200CC of an aqueous solution in which 14 equivalents of Na0HO are dissolved.
was added dropwise while stirring.
生じた沈澱を濾過と水洗を繰り返した後に乾燥し、粉砕
することにより、当量比１対４のポリアクリル酸スズの
粉末を得た（粉末■）。The resulting precipitate was repeatedly filtered and washed with water, then dried and pulverized to obtain a tin polyacrylate powder with an equivalent ratio of 1:4 (powder ■).
製造例７
重合度５，０００のポリアクリル００．１当量が溶解Ｌ
テイル水ｆ８Ｈ５００ＣＣ中Ｋ、ＴｉＣｌ２、ＡｔＣ
ｌ３、ＣａＣｌ２がそれぞれ０．０２５当量、０．０５
当量、０．０２５当量溶解している水／エタノール（１
９／１）混合＠液３００ＣＣを攪拌しつつ滴下した後に
、Ｎａ ＯＨＯ、１当量が（ｆＪｍしている水−ｇｙｆ
ｆｌ ２００ωを攪拌しつつ滴下させた。Production Example 7 00.1 equivalent of polyacrylic with a degree of polymerization of 5,000 is dissolved L
Tail water f8H500CC medium K, TiCl2, AtC
l3, CaCl2 are 0.025 equivalent and 0.05, respectively.
equivalent, 0.025 equivalent dissolved water/ethanol (1
9/1) Mixed @ After dropping 300 cc of liquid while stirring, 1 equivalent of Na OHO was (fJm water - gyf
fl 200Ω was added dropwise while stirring.
生じた沈澱を濾過と水洗とを操り返した後に乾燥し、粉
砕することにより、当量比１対１のポリアクリル酸のチ
タン、アルミニウム、カルシウム混合金４塩を得た（粉
末■）。The resulting precipitate was filtered and washed with water, dried, and pulverized to obtain a mixed gold tetrasalt of polyacrylic acid with titanium, aluminum, and calcium in an equivalent ratio of 1:1 (powder ■).
製造例８
重合度５，０００のポリアクリル酸０．１当量が溶解し
ている水溶液５００ＣＣ中に、５ｎｃｔ４、Ｚｎｃｔｚ
がそれ・ぞれ０．０５当量、０．１５当量ｍ解している
水／エタノ−＃（１９／１）混合１６Ｍ３ｏｏｅｃ、を
攪拌しつつ滴下した後に、ＮａＯＨＯ，２当量が溶解し
ている水溶液２００ＣＣを攪拌しつつ滴下させた。Production Example 8 In 500 CC of an aqueous solution in which 0.1 equivalent of polyacrylic acid with a degree of polymerization of 5,000 was dissolved, 5 nct4, Znctz
0.05 equivalent and 0.15 equivalent, respectively, of water/ethanol # (19/1) mixed 16M3ooec were added dropwise with stirring, followed by an aqueous solution in which 2 equivalents of NaOHO were dissolved. 200 CC was added dropwise with stirring.
生じた沈殿を濾過と水洗を、操り返した後に乾燥し、粉
砕することにより、当量比１対２のポリアクリル酸のス
ズ、亜鉛混合金属塩を得た（粉末■）。The resulting precipitate was filtered and washed with water, dried, and pulverized to obtain a mixed metal salt of tin and zinc of polyacrylic acid with an equivalent ratio of 1:2 (powder ■).
ポリアクリル酸金属塩の生成は、Ｘ線回折（金属酸化物
、金、４水酸化物、金属塩化物のピークが現れない）お
よび赤外吸収スペクトル（１７００ｉ１の＞ｃｏの吸収
がなくなり、１５ 、） ０ｅｙｎ に金属塩の生成
による吸収ピークが現れる）により確認した。The production of polyacrylic acid metal salts can be seen in X-ray diffraction (metal oxide, gold, tetrahydroxide, and metal chloride peaks do not appear) and infrared absorption spectrum (1700i1>co absorption disappears, 15, ) An absorption peak due to the formation of metal salts appears at 0eyn).
実施例１
製造例１で得た粉末Ｉを１．６ｔとり、これを第１図に
示す金型のハウジング材（２，２）と内径２Ｉｙｎのシ
リンダー（４）より形成されるキャビティ（１）に充填
した。Example 1 1.6 tons of powder I obtained in Production Example 1 was taken and poured into a cavity (1) formed by the mold housing material (2, 2) and the cylinder (4) with an inner diameter of 2 Iyn as shown in FIG. was filled.
ついで排気管α〔よりキャビティ内の空気を真空ポンプ
を用いて排気しつつ、２００℃で６０分、ｓ、ｏ ｏ
ｏ ｔｓ／−の圧力を加えて成形し、ついで室温まで冷
却して肉厚３ＩＩｌ＋１１１ 径２０晒の円板を得た。Next, the air inside the cavity was evacuated from the exhaust pipe α using a vacuum pump, and the air was heated at 200°C for 60 minutes, s, o o.
It was molded under a pressure of 0 ts/-, and then cooled to room temperature to obtain a disk with a wall thickness of 3II+111 and a diameter of 20 mm.
この円板は、比重が１．６７であり、薄茶色に着色して
いたものの透明体であった。This disk had a specific gravity of 1.67 and was colored light brown but was transparent.
この円板全長さ１５酎、：＠８０、厚さ２咽の直方体に
切削し、島津製作所■裂オートグラフを用い、０．５ｍ
ｍ／、％のクロスヘッドスピードで２０℃にしける圧縮
弾性率を測定したところ、１６．６ギガパスカル（ＧＰ
ａ）であった。This disk has a total length of 15 mm, is cut into a rectangular parallelepiped with a thickness of 2 mm, and is 0.5 m long using a Shimadzu ■Crack autograph.
The compressive elastic modulus at 20°C was measured at a crosshead speed of 16.6 gigapascals (GP
It was a).
また、これと直角方向の圧縮弾性率！ｄ１６．ＩＧｐａ
でろった。Also, the compressive elastic modulus in the direction perpendicular to this! d16. IGpa
It turned out.
実施例２〜８
粉末■〜■を衣１に示す量、・皿内に充スし、同表に示
す成彩条件で加圧成形を行なって同表に示す゛物性の成
形体を得た。Examples 2 to 8 Powder ■ to ■ were filled in a dish in the amount shown in Clothing 1, and pressure molded under the coloring conditions shown in the same table to obtain a molded product with the physical properties shown in the same table. .
比紋例１
重合９３，５００のポリアクリル酸の微分１モルと、Ｔ
ｉ ０２の：故扮１／４モルとの、見合粉末を、２５０
℃で随時圧抜きしつつ１００ ｋｇ／ ｃｒｄから８０
０ ｋ７／−まで６０分かけて加圧したが、ポリアクリ
ル酸とＴｉＯ２は反応せず、ポリアクリル酸チタンの成
形体は得られなかった。Ratio example 1 1 mole of differential polyacrylic acid with polymerization 93,500 and T
i02: 1/4 mole of powder, 250
℃ from 100 kg/crd to 80 while releasing pressure from time to time.
Pressure was applied to 0 k7/- over 60 minutes, but the polyacrylic acid and TiO2 did not react, and no titanium polyacrylate molded body was obtained.
（以下余白）(Margin below)
ｉｔ図は実施例１で用いた加圧装置の断面である０
１−Ｑ科、２−ノ・ウジング部材、３−、ヒ邪ピストン
棒、４−シリンダー、５−ｏリング、６−０リング押え
、７−外筒、８−外筒上部、９−外筒下部、１〇−排気
バイブ。The IT diagram is a cross section of the pressurizing device used in Example 1. Presser foot, 7-outer cylinder, 8-outer cylinder upper part, 9-outer cylinder lower part, 10-exhaust vibrator.
Claims (4)
金属が１０〜１００モル％で、１価および／または２価
および／または３価の金属が９０〜０モル％であるポリ
アクリル酸金属塩の粉末を型内に充填後、１００ｋｇ／
ｃｍ＾２以上１００万ｋｇ／ｃｍ＾２以下の圧力で、か
つ、該ポリアクリル酸金属塩の融点より低い温度条件で
加圧成形して成形体とすることを特徴とするポリアクリ
ル酸金属塩の成形体の製造方法。(1) Polyacrylic acid in which the metal constituting the polyacrylic acid metal salt is 10 to 100 mol% of a tetravalent metal and 90 to 0 mol% of a monovalent and/or divalent and/or trivalent metal. After filling the acid metal salt powder into the mold, 100kg/
A polyacrylic acid metal salt, which is formed into a molded product by pressure molding at a pressure of cm^2 or more and 1 million kg/cm^2 or less and at a temperature lower than the melting point of the polyacrylic acid metal salt. A method for producing a molded article.
特許請求の範囲第１項記載の製造方法。(2) The manufacturing method according to claim 1, wherein the pressure molding is performed under reduced pressure.
を特徴とする特許請求の範囲第１項記載の製造方法。(3) The manufacturing method according to claim 1, wherein the pressure molding is performed at a temperature of 50 to 500°C.
測定した圧縮弾性率が１５〜４０ギガパスカル（ＧＰａ
）以上であることを特徴とする特許請求の範囲第１項記
載の製造方法。(4) The compressive elastic modulus of the molded body measured in accordance with JIS K7208-1975 is 15 to 40 gigapascals (GPa).
) or more.The manufacturing method according to claim 1.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26935585A JPS62259818A (en) | 1985-12-02 | 1985-12-02 | Mafnufacture of molded body of polyacrylic metal salt |
| US06/893,924 US4732721A (en) | 1985-09-30 | 1986-08-06 | Method for production of shaped bodies of metal salts of polyacrylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26935585A JPS62259818A (en) | 1985-12-02 | 1985-12-02 | Mafnufacture of molded body of polyacrylic metal salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62259818A true JPS62259818A (en) | 1987-11-12 |
| JPH0134770B2 JPH0134770B2 (en) | 1989-07-20 |
Family
ID=17471222
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26935585A Granted JPS62259818A (en) | 1985-09-30 | 1985-12-02 | Mafnufacture of molded body of polyacrylic metal salt |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62259818A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5486573A (en) * | 1992-06-30 | 1996-01-23 | Toyota Jidosha Kabushiki Kaisha | Polymer powder cross-linked by metallic ions and containing reinforcing material, process for producing the polymer powder, composite material based on polymer cross-linked by metallic ions, and process for producing the composite material |
-
1985
- 1985-12-02 JP JP26935585A patent/JPS62259818A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5486573A (en) * | 1992-06-30 | 1996-01-23 | Toyota Jidosha Kabushiki Kaisha | Polymer powder cross-linked by metallic ions and containing reinforcing material, process for producing the polymer powder, composite material based on polymer cross-linked by metallic ions, and process for producing the composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0134770B2 (en) | 1989-07-20 |
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