DE19736850A1 - Curable plugging material for fixing anchor bars in bore holes - Google Patents

Abstract

A curable plugging compound with improved adhesion and long-term stability is based on a compound with hybrid functionality, containing (a) polymerisable unsaturated end group(s) and (b) substituent(s) with different reactivity to that of (a) under usage conditions.

Description

Curable dowel compounds based on vinyl ester resins are known (EP 0 150 555; EP 0 199 671 and EP 0 432 087). They stand out over the previously customary curable, unsaturated polyester resins their superior adhesive strength and long-term durability even under chemically aggressive conditions. Here, too, you stand in line their known, chemically setting dowel masses always as before the way in which chemical adhesion between the materials of the fastener and the receiving material can develop and have built up when setting the dowel masses. When holding a fastener in a dowel bed in the Drill hole of a recording material are on a relatively small area very high static and dynamic loads and movements brings. Therefore, high adhesion values must be in addition to good long tent stabilizers quality and aging behavior of a dowel compound. The critical parameters and thus the weak points in such a Be fastening system represent the interfaces between the fastening element and dowel mass bed on the one hand and mounting material and dowel mas sen bed on the other hand. At the interface fastener / nozzle the mass can be bonded via a mechanical adhesion be improved by opening up the surface of the fastener is roughened, corrugated or threaded. When recording Such manipulations are difficult to carry out and become due to dust dust adhering to the borehole walls or Water also negatively affected, because this only with great effort are removable.

One of the objects of the present invention is the Ver improvement of the known dowel masses both in their shelf life and also in their adhesive strength and long-term durability.

The invention solves the aforementioned problems by hardening dowel mats with a content of a hybrid functional compound according to Pa claim 1. It is preferably the terminal remainder a) an ethylenically unsaturated acid residue.

Under hybrid function in the present sense, connections are hereby  gene understood that like the rest a) and substituent b) two functional have different groups, which are different Network, harden and / or have reaction mechanisms networked.

There are already known hardenable vinyl ester dowel compounds additionally up to 10% by weight of bisphenol A epoxides to improve the La ger stability included (DE-OS 36 38 750). The epoxides work here they cannot be polymerized into the vinyl conductor matrix like a soft makers, which has a rather negative effect on long-term behavior.

Dowel compounds with a hybrid-functional compound of the formula are preferred

wherein
R is the hydrocarbon radical of an ethylenically unsaturated, optionally hydroxyl, nitrile, halogen and / or C ₁ -C ₄ alkyl-substituted carboxylic acid derivative, preferably an acrylic, methacrylic and / or crotonic acid derivative,

X = -O-, -N (R ² ) -, -NH-C (O) - and / or

the groups RC (O) -X- represent an ethylenically unsaturated dicarboxylic acid residue, preferably maleimide residue,
R ^{1 is} an optionally substituted, in particular hydroxy, amino, halogen, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy and / or oxy-C ₁ -C ₄ alkyl-substituted, saturated or unsaturated hydrocarbon residue, preferably a C ₁ -C ₁₀ aliphatic or cycloaliphatic hydrocarbon residue, and optionally

-C (O) -O-, -OC (O) -, -O-, -C (O) -, -NH-C (O) -NH-,

and / or -NH-C (O) - bridge members,
Y is a substituent which contains an oxirane or epoxy group or a reactive, preferably inorganic, oxygen acid radical,
R ^{2 can be} H, RC (O) -, -R ¹ -Y _m and / or C ₁ -C ₄ alkyl,
n = 1 to 5,
m = 1 to 5.

Compounds in which R is an allyl- or vinyl group.

The hydrocarbon radical R ¹ can be aliphatic, cycloaliphatic or aromatic, with the substituents or bridge members mentioned, for. Belly

and / or, if X is not oxygen, be an aromatic compound of the general formulas

or

wherein R ³ and R ⁴ , H, alkyl, alkoxy each having 1-5 C atoms and / or R-C (O) -, R ⁵ alkyl, p = 1 or 2 and R ^{6 is} an optionally substituted C ₁ -C ₅ -hydrocarbon residue or an oxygen or nitrogen-containing bridge member.

The substituent Y is in particular a given on the carbons, if necessary. B. hydrocarbon-substituted group of formula

or an acid residue of the formula

wherein Z is phosphorus, sulfur or Is carbon and s = 1, 2 or 3.

A particular advantage of the dowel compounds according to the invention is in that the two different functionalities in the resin matrix are integrated without the risk of migration of one of the functionaries  and at the same time the adhesion to different material surfaces chen z. B. also receiving material and storage stability improved become. The hybrid functional compounds can, if necessary in addition to other reactive components, in the dowel masses in quantities 1 to 95% by weight, in particular 5 to 65% by weight, based on the total weight of the dowel mass, be included. You can also join others known dowel compounds for improving adhesion z. B. in quantities from 1 to 35% by weight, based on the total dowel mass, may be added.

If the substituent b) contains a reactive epoxide, compounds with ω-epoxy groups are particularly preferred. Examples of suitable connections are
α, ω, -hydroxy-alkyl- (meth-) acryloyl- or allyolyl-oxiranes; α, ω-isocyanate alkyl (meth) acryloyl or allyloyl oxiranes; ω-alkenyloxy-alkoxy-alkyl (meth) acryloyl- or allyloyloxiranes. You can e.g. B. by additions and condensations of hydroxymethyloxirane on or with isocyanates, acrylic acid derivatives, vinyl sulfonates and the like can be obtained. Examples of such compounds include methyl acrylate (oxiranylmethyl ester), 2,4-dioxo-1- (oxiranylmethyl) -3-methacryloyl- or 3-acryloyl-2,4-dioxo-1- (oxiranylmethyl) imidazolidine, monoepoxidized isoprene , Allyloxymethyl-oxirane, maleic acid or furmar acid-bis- [oxiranylmethyl ester], 2,4-hexadienoic acid (oxiranylmethyl ester), 4-vinyl-benzoic acid (oxiranylmethyl ester), acrylic acid (allyl oxiranylmethylamide), (diallylamino methyl) oxirane-2,2-bis- [3-allyl-4-oxiranyl-methoxyl-phenyl] propane; (α, ω-vinyloxy-alkoxymethyl) oxira ne,
e.g. B. 2- (4-vinylmethoxyphenyl) -2- (4-oxiranylmethoxyphenyl) propane; cycloaliphatic oxiranes with at least one ethylenically unsaturated group, such as. B. 4-Hydroxy-5-methacryloyl-2-methylcyclohexane carboxylic acid (4,5-epoxy-2-methylcyclohexyl methyl ester); 8-hydroxy-9-acryloxy-3- (3,4-epoxycyclohexyl) -2,4-dioxa-spiro [5.5] undecane; 1- (methyl-acryloxy-2-hydroxypropoxy-methyl) -4- (oxiranylmethoxymethyl) cyclohexane; dicycloaliphatic oxiranes with e.g. B. an ethylenically unsaturated group, being of the general formula

correspond in which B is a radical of the general formula

is and R, R ₁ , X and n have the above meaning. Examples of such compounds are dicyclopentadienyl (acryloyl-2-hydroxypropoxy) bis (methoxyoxirane); Dicyclopentadienyl- (methacryloyl-2-propoxy-methoxy) - (methoxymethyloxirane): methacryloyl-dicyclopentadienyloxirane; Methacryloylethoxy-dicyclopentadienyloxirane; 3-hydroxy-4-methacrylicyl-cyclohexylmethoxydicyclopentadienyloxirane; Methacryloyl-bis (dicyclopentadienyl) oxy-oxirane.

The above described and other analogous compounds with Hy brid functionality are described in the literature. Due to the hy Bride functionality, these connections are also different Reaction mechanisms can be hardened or cross-linked. So the ethyle nically unsaturated groups free radical by means of peroxides z. B. Tue. benzoyl peroxide, cumene hydroperoxide and optionally with amine or Heavy metal accelerators such as diethylaniline, diethyl-p-toluidine, Co baltoctoate, vanidyl p-toluenesulfonate or by blasting and the oxirane groups either with compounds that have active H atoms or ka tionally with UV rays, e.g. B. harden in the presence of Lewis acids or network. The networking processes can be carried out individually or together be performed.

The chemical adhesion of the dowel materials according to the invention mostly metallic material of the fastener z. B. Anchors rod and the regular mineral absorption material is special more pronounced when the substituent b) react with the substrate the acid residue, namely an acid residue of an inorganic acid. It is acids that z. B. with silicates, aluminates, Alka Li and / or alkaline earth aluminum silicates, natural or synthetic Provenance make insoluble or poorly soluble compounds. Especially ders are suitable here instead of other acid residues as an example called acid residues of phosphorus and sulfur.

Ent as the substituent b) sulfuric acid residues or phosphoric acid residues holding connections characterize the dowel compounds according to the invention  through improved adhesive properties, better thermal stability or reduced flammability, corrosion resistance and higher bond strength out. Inorganic binders, e.g. B. cements such as port Land cement that is hydraulic and / or polycondensing in the presence bind from water, often contain z. B. Alkaline earth compounds.

About the acidity potential of the OH group on the phosphorus atom or Sulfur atom can u. a. with alkaline earth oxide or alkaline earth salt content against absorbent materials, such as those used in construction for many building materials lie, e.g. B. build insoluble salt bridges. The same applies to me tallen materials.

The ethylenically unsaturated groups in the hybrid functional molecule In contrast, compounds either crosslink through polymerization with itself or with other unsaturated components, such as. B. Vi nyl esters (epoxy acrylates), vinyl urethanes, reactive solvents etc. The oxirane substituents can continue with H-active substances Make bonds.

The hybrid dowel compounds can be so-called semiinter when setting form penetrating networks. This allows the inorganic Include binders chemically in the organic network. Such Anchoring compounds have the advantage that they can be used on wet as well as on Drill dust contaminated borehole surfaces can be used.

The invention makes dowel masses accessible via bridge members chemical adhesion to both the fastener and Form the receiving material and thus to the desired chemi can lead to material closure. Examples more useful in or as sub stituents b) contained phosphoric acid residues are phosphinic acids, Phosphonic acids, phosphoric acids, phosphonous acids, phosphinous acid ren or phosphoric acids.

The acid residues are the phosphorous and the hypophosphorous To name acid, but also diphosphines. In the rest of the Phos  phosphoric acid substituents b) should have at least one reactive acidic H and / or HO group for reaction with cations, e.g. B. from the 2nd group of the periodic table to have hybrid hardening functions besides the ethylenically unsaturated group.

Examples of the compounds according to the invention include:

• - Di- (meth) acryloyloxyethylphosphinic acid
• - (Meth) acryloyloxypropylphosphonic acid
• - (Meth) acryloyloxyethyloxymonophosphoric acid
• - (Meth) acryloyloxyethyloxydicylcopentenyloxymonophosphoric acid
• - (Meth) acrylic acid (2-ethyloxyphosphoryloxyethyl ester)
• - (Meth) acrylic acid- (2-phospho-1,1-dimethylethylamide)
• - Phosphorous acid (2-acryloyloxyester) phenyl ester
  

The polymerization behavior of the hybrid functional compounds with Phosphoric acid residue also depends on the distance between ethyleni sure group and P atom. Is the P atom by multiple atoms or Atomic groups can also be removed from the C-C double bond receive high molecular weight polymers. In contrast, the P atom is closer to the C-C double bond bonded, polymers with gerin are preferred get molar masses. The former monomers are preferred. The hybrid functional phosphor monomers or prepolymers can both ho be copolymerized as well. There can be polymers with molecular weights up to 1,000,000.

The phosphorus residue substituent b) in the connections of the dowel compound is suitable for implementation with alkaline earth metals and aluminum ones in particular Connections, for which virtually all bind hydraulically  the cements and silicates are suitable. But also polycondensing Silicates, kaolin, metakaolin and the like are suitable.

Sulfonic acid residues also serve as reactive acid residues, e.g. B. Connections such as (meth) acryloylethylene monosulfonic acid.

Residues of organic carboxylic acids ho are also suitable as acid residues b) forth acidity, especially acetic acid, propionic acid or formic acid remnants.

The hybrid functional compounds can be used alone or in combination with other ethylenically unsaturated compounds in the inventive Dowel compounds or as adhesion promoters in chemically binding The dowel masses must be included. Ethylenically unsaturated verb are z. B. reactive diluents and / or crosslinking agents such as acrylic and methacrylic compounds bearing ethylenically unsaturated groups Vinyl esters, polyurethanes, epoxy acrylates, trimethylolpropane tri methacrylate, bis-phenol-A-diethoxy-dimethacrylate, dicyclopentenyl ethyloxymethacrylate, siloxane dimethacrylate, styrene and the like.

As for the polymerization of all of the dowel materials according to the invention contained hybrid functional compounds are also the pre named compounds with epoxides as reactive substituents b) with the known initiator and accelerator systems, such as tert. Ami NEN, active H-atom-providing compounds, CaO and / or high-energy Radiation hardened or cross-linked. To bind or implement the Acid residues as substituents b) generally do not become reactions initiators needed. The acidity of the compound or the alkalinity of the substrate. Is the substituent an oxirane or epo xid, this group can coordinate coordination with the calcium oxide of the receiving materials. Because the oxirane or epoxy group is chemically bound to the resin matrix, in contrast to the DE- Do not migrate OS 36 38 750.  

The dowel masses can also known components such as Contain fillers, dyes, pigments and / or plasticizers. she can u. a. as usable in the borehole bicameral systems, e.g. B. as Cartridges that contain the hardenable components from the hardeners through Setting conditions of destructible walls contain separately assembled or as a foil pack, with curable components and hardeners are contained in two different foil bags and via mixing nozzles be injected into the borehole.

Examples

The two-component dowel materials according to the invention are described in be knew packed two and multi-chamber devices. You can ever but can also be formulated as quasi one-component dowel compounds, in that of the hardener, such as. B. benzoyl peroxide, in microencapsulated form in the Resin mixture is incorporated homogeneously.

example 1 Component A

35.0 parts by weight of bisphenol A diglycidyl methacrylate
10.0 parts by weight of methacryloyloxyethyloxymonophosphoric acid
0.5 part by weight of diethylaniline
3.5 parts by weight of silica, pyrogenic
51.0 parts by weight

Quartz sand 0.1 to 0.3 mm
100.0 parts by weight of component A

Component B Dibenzoyl peroxide, 50% in phthalate plasticizer

Mixing ratio:
Component A: 100 parts by weight
Component B: 5 parts by weight

Example 2 Component A

30.0 parts by weight of bisphenol A diglycidyl methacrylate
10.0 parts by weight of methacryloylethoxydicyclopentadienyloxirane
0.4 parts by weight of diethylaniline
2.6 parts by weight of silica, pyrogenic
57.0 parts by weight

Quartz sand 0.1 to 0.3 mm
100.0 parts by weight of component A

Component B Dibenzoyl peroxide, 20% in phthalate plasticizer

Mixing ratio:
Component A: 100 parts by weight
Component B: 10 parts by weight

Example 3 Component A

40.0 parts by weight of bisphenol A diglycidyl methacrylate
5.0 parts by weight of methacryloyloxyethyl monosulfonic acid
5.0 parts by weight of dicyclopentadienyl methacrylate
2.5 parts by weight of silica, pyrogenic
0.5 part by weight of diethylaniline
3.0 parts by weight of hemp fiber pulp
44.0 parts by weight

Quartz sand 0.1 to 0.3 mm
100.0 parts by weight of component A

Component B Dibenzoyl peroxide, 20% in phthalate plasticizer

Mixing ratio:
Component A: 100 parts by weight
Component B: 10 parts by weight

Production of the dowel masses

The Vinylest are in a vacuum planetary mixer with dissolver equipment Resin and the hybrid-functional compounds presented and pre-homogeneously mixes. Then you work the diethylaniline (accelerator) and the pyro of silica and disperses the batch with the dissolver equipment. To the Finally, the quartz sand is poured into the Mass incorporated. Before filling, the homogeneously mixed dowel mass degassed under vacuum.

Claims (8)

1. Curable dowel mass, characterized by a content of a hybrid functional compound that

• a) on the one hand at least one polymerizable, terminally ethylenically unsaturated radical and
• b) on the other hand, at least one substituent which is reactive under application conditions from a)

having. 2. Curable dowel mass according to claim 1, characterized records that the residue a) is an ethylenically unsaturated acid residue. 3. Curable dowel mass according to claim 1 or 2, characterized ge indicates that the substituent b) contains reactive epoxy. 4. Curable dowel mass according to claim 1 or 2, characterized ge indicates that the substituent b) contains a reactive acid residue. 5. Curable dowel compound in particular according to one of the preceding claims, characterized by the content of a hybrid functional compound of the formula
wherein
R is the hydrocarbon radical of an ethylenically unsaturated, optionally hydroxyl, nitrile, halogen and / or C ₁ -C ₄ -alkyl-substituted carboxylic acid derivative, preferably an acrylic, methacrylic and / or coton acid derivative,
X = -O-, -N (R ² ) -, -NH-C (O) - and / or
the group RC (O) -X- stands for an ethylenically unsaturated dicarboxylic acid residue, preferably maleimide residue,
R ^{1 is} an optionally substituted, in particular hydroxy, amino, halogen, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy and / or oxy-C ₁ -C ₄ alkyl-substituted, saturated or unsaturated hydrocarbon residue, preferably a C ₁ -C ₁₀ aliphatic or cycloaliphatic hydrocarbon residue and optionally C (O) -O-,
-OC (O) -O-, -OC (O) -, -O-, -C (O) -, -NH-C (O) -NH-,
and / or -NH-C (O) - bridge members,
Y is a substituent which contains an oxirane group or a preferably inorganic oxygen acid radical
R ² = H, RC (O) -, -R ¹ -Y _m and / or C ₁ -C ₄ alkyl,
n = 1 to 5
m = 1 to 5. 6. Curable dowel mass according to one of the preceding patent sayings, characterized in that the substituent b) one with the Intake material contains reactive acid residue. 7, Curable dowel mass according to one of the preceding patent sayings, characterized in that the substituent b) a Schwe rock acid residue or the rest of a phosphoric acid. 8. Use of the dowel mass according to one of the preceding Pa Tent claims for fastening anchor rods in boreholes.