The subject of this invention is a process for the manufacture of polymeric materials with a high chemical and mechanical resistance, par¬ ticularly suitable in chemical, electrochemical and non- ferrous metals industries, as well as a polymeric material with a high chemical and me- chanical resistance.

It is c rmonly known that synthetic resins are used either as binders in building materials such as mortars and concretes or as compo¬ nents of chemo- or thermosetting composites containing in their cccαpo- sition fillers being many a time industrial wastes such as sawdust and smoke-box ashes. Thus, Polish Patent Specification no. 65677 discloses a floor mix containing 30-40 % of polyester resins, about 5 % of e- poxide resins, 55-65 % of mineral fillers and an accelerant and hard-

3 ener, the whole showing a mass density of 2.2 kg/dm. There is also known a floor mix containing 100 parts of epoxide resins, 5-20 parts vegetable epoxy oil, 10-20 parts of xylene, 8-12 parts of triethanol- amine, 200-400 parts of kermesite with a grain size of up to 5 mm and

20-150 parts of dry microspheres with a bulk density of 0.35-0.42

3 kg/dn, thermal conductivity 0.04-0.1 W/mK and ccrnpression strength

30-35 MPa. There are also cαnuunly known problems in utilization of industrial wastes, including waste phosphogypsum resulted in conside¬ rable amounts from the manufacture of phosphoric acid from apatites. One of the utilization processes, in accordance with Polish Patent Spe¬ cification no. 119692, consists of elimination of radium, uranium, fluorine and phosphorous cctnpounds from phosphogypsum through deccmpo-

RECTIFIED SHEET (RULE 91) ISA/EP

sition by means of phosphoric acid. Another process, according to Pol¬ ish Patent Application no. P.287016, concerns the manufacture of gyp¬ sum from waste phosphogypsum by adding about 6 parts by weight of waste ferrous sulphate and about 4.7 parts by weight of barium chloride to 1000 parts by weight of waste phosphogypsum, and then calcinating the mixture with quicklime at temperature 350-500 K. Another Polish Patent Specification no. 147599 discloses the manufacture of building phosphogypsum materials ccmprising the preparation of a binding slurry by mixing a -thermally treated phosphogypsum with make-up water and adding antiefflorescent agents in the form of sulphonated polyconden- sating resins, organic and inorganic silicon salts alkali metals. It is also known from Polish Patent Application no. P.283240 that waste phosphogypsum can be ccmbined with polyester resins to prepare a mate¬ rial which is characterizes by good mechanical and chemicεil resistance and low water and oil absorptions. According to Polish Patent Applica¬ tion no. P. 299472 and P. 299473, it is also possible to combine, in an anhydrous system, epoxide resins and/or polyester resins with phos¬ phogypsum or phosphogypsum and glass-forming oxides or phosphogypsum and magnetite to prepare ceramic-like materials with special properties including good mechanical and chemical resistance, being easily forπable, especially by casting, and showing good adherence to various materials such as wood, metals, glass, and susceptible to processing by machining, grinding and cutting, and suitable for a wide application. There is also known from US Patent Specification no. 3873492 a process for the manu- facture of a mixed materials containing gypsum and a thermoplastic resin; the gypsum to be used for the mixture is previously powdered and impreg¬ nated with a polysulphone resin.

It has unexpectedly appeared that using waste phosphogypsum, but only after its previous ttermal treatment, in a composition with vinyl-

SUBSTITUTE SHEET

3 ester resins, one can prepare materials with a very high resistance both to acidic and alkaline media, showing water absorption below 0.5 %,

2

Charpy impact strength over 1.55 kJ/m , bending strength over 15 MPa, cαnpression strength over 75 MPa, thermal conductivity index below 0.485 W/mK, the materials being also safe to health and showing a ra¬ dioactivity level corresponding to that of cement and red bricks. More¬ over, when glass-forming oxides are added to the materials they are characterized by ability to absorb X-radiation with an energy of 45-55 keV and hard radiation with an energy of 0.6-1.25 MeV; if magnetite is added to the cαnposition, the materials shew magnetic properties and when microsphere is added to the cαnposition, the resultant material is characterized by a low thermal conductivity and a density of belcw

3 0.8 kg/dm .

Itie process for the manufacture of materials with a high chemical and mechanical resistance by polymerization of a mixture of a synthetic resin with an inorganic filler in the presence of accleerants and poly¬ merization initiators, in an anhydrous medium, according to the present invention consists in that to each 100 parts by volume of vinylester resin, treated with 0.85-1.47 parts by volume of an accelerant in the form of a styrene solution of cobalt naphthenate, 50-900 parts by vo¬ lume of waste phosphogypsum previously roasted at a temperature not le¬ ver than 470 K and disintegrated to a particle size of below 30 μm, with a bulk density of 0.71-0.93 kg/dm , are added while continuous stirring, at least in two batches, and if necessary up to 60 parts by volume of styrene and/or a low-molecular-weight unsaturated polyester resin and/or up to 0.2 parts by volume of djj∞thylaniline are also ad¬ ded. Next, on continuous stirring, to the physicochemicεtlly hemogenized cemposition a known organic peroxide in a quantity of 6.3-7.3 parts by volune is added as polymerization initiator, to obtain 130-780 parts

SUBSTITUTE SHEET

by volume of a material resistant to the action of acids and bases, both concentrated and diluted ones , with an impact -strength of over 1.85

2 kJ/m , bending strength over 35.4 MPa, compression strength over 106

MPa and water absorption below 0.61 %. The resultant material, due to its properties, is perfectly suitable to make floors in rooms, including also accoπiπodations under conditions occuring in chemical and electroche¬ mical industries and in non-ferrous metal works, especially in depart- mens of electrolytic refining.

In order to obtain the material in a form suitable for applica- tion, especially by the hydrodynamic method, as antiσorrosive or pro¬ tective coats, the physicochemically homogenized composition of vinyl¬ ester resin with phosphogypsum is additionally processed similarly as in the manufacture of paints and lacquers, preferably in fine grinding mills with continuous operation, until the particle size in the cσmposi- tion is belcw 7 μm,then styrene in a quantity of up to 2.5 % by volume and/or a low-molecular-weight unsaturated polyester resin in a quanti¬ ty of up to 5 % in relation to the volume of the whole mixture cure ad¬ ded. Next, polymerization initiators are added to produce a material suitable for spraying onto surfaces and allowing in a single spray the formation of a coat with a thickness of atleast 250 μm, which means a coat thickness feasible in using known coats not before at least two and usually four or five spraying runs.

The material with a high c±iemical and rnechanical resistance, con¬ stituting a polymerized composition of synthetic resin and an inorganic filler, according to the present invention consists of 11.6-77.1 % by weight of vinylester resin, 14.3-86.8 % by weight of waste phosphogyp¬ sum, 0.67 -3.74 % by weight of an organic peroxide and up to 29 % by weight of styrene and/or a lo -molecular-weight unsaturated polyester resin.

SUBSTITUTE SHEET

A modification of the process for the manufacture of the material according to the present invention consists in adding, as an inorganic filler, at least in two batches, either previously roasted phosphogyp¬ sum alternately with glass-forming oxides or a physically homogenized dry composition or roasted phosphogypsum and glass-foπning oxides con¬ sisting mainly of lead, silicon and barium oxides with particle size up to 25 μm and a bulk density of 3.9-4.1 kg/dm , with the weight ratio of phosphogypsum to glass- forming oxides being as 1 : 0.7-1.5. The ad¬ dition of glass-forming oxides as a component to the inorganic filler makes it possible to produce a material which is capable to attenuate or absorb X-radiation with an energy of 0.55 keV and hard radiation with an energy of 0.6-1.25 MeV. In the case when the material is to be used as protective coating capable to attenuate or absorb the above mentioned radiation, the physiαx-hemically σcmposition of vinylester resin with phosphogypsum is additionally processed similarly as in manufacturing paints and lacquers, preferably in continuously operated fine grinding mills until the particle size is 7 μm and then 2.5 % by volume of sty¬ rene and/or up to 5 % by volume of a low-πolecular-weight unsaturated polyester resin are added, after which polymerization initiators are ad- ded. The resultant material is characterized by a very good fluidity at the initial stage of polymerization, which facilitates its use for coat¬ ing elements to be used as shields or screens protecting againts radia¬ tion and requiring anticorrosive protection.

The material capable to attenuate and/or to absorb X-radiation with an energy of 55 keV and hard radiation with an energy of 0.6-1.25 MeV, constituting a polymerized composition of a synthetic resin and an inorganic filler, according to the present invention consists of 10.1-79.8 % by weight of vinylester resin, 5.8-43.9 % by weight of roasted waste phosphogypsum, 6.4-44.8 % by w≡ ght of glass-forming ox-

SUBSTITUTE SHEET

ides, containing mainly lead, silicon and barium oxides, 0.58 -3.89 % by weight of an organic peroxide and up to 29.8 % by weight of styre¬ ne and/or a low-molecular-weight unsaturated polyester resin.

Another modification of the process for the manufacture of the material according to the present invention consists in that there is added as an inorganic filler, at least in two batches, either previous¬ ly roasted phosphogypsum alternately with a microsphere or a previously physically homogenized dry composition of roasted phosphogypsum and mi¬ crosphere, with a particle size of belcw 25 μm, with the weight ratio of phosphogypsum to microsphere being as 1 : 0.43 -45. In order to pre¬ pare a material in a form suitable for applying as anticorrosive or pro¬ tective coats, an inorganic filler with a particle size of below 7 μm is used. The addition of microsphere as a component of the inorganic filler makes it possible to produce a material also with density of be- low 0.8 kg/dm , being very resistant to chemical nad showing thermal conductivity below 0.24 W/mK, water absorption below 0.24 %, which is particularly suitable for use in yacht- and shipbuilding industry, including protective and anticorrosive coatings.

The material in the form of a polymerized composition of a syn- thetic resin and an inorganic filler, according to the present inven¬ tion consists of 7.5-88.1 % by weight of vinylester resin, 0.4-38.2 % by weight of roasted waste phosphogypsum, 4.6-53.5 % by weight of mi¬ crosphere, 0.43-4.40 % by weight of an organic peroxide and 34.1 % by weight of styrene and/or a low-irolecular-weight unsaturated poly- ester resin.

Still -mother modification of the process for the manufacture of the material according to the present invention consists in adding, as an inorganic filler at least in two batches, either previously roasted waste phosphogypsum alternately with magnetite or a physically hα-noge-

RECT1FIED SHEET (RULE 91) ISA/EP

nized dry composition of previously roasted phosphogypsum and magnetite, with the weight ratio of phosphogypsum to magnetite being as 1 : 0.6-1.3. In order to produce a material suitable for hydrodynamic application, the physiccchemically hcmogenized composition of vinylester resin, phospho- gypsum and magnetite is processed similarly as in the manufacture of paints and lacquers, preferably by grinding in continuously operated mills. The resultant material, due to its high c±temical resistance and very good mechanical properties as well as magnetic properties, is per¬ fectly suitable for using in microelectronics, especially for manufac- turing electronic microelements to be exposed to corroding media.

The material in the form of a polymerized composition of a syn¬ thetic resin and an inorganic filler, according to the present inven¬ tion consists of 10.1-80.1 % by weight of vinylester resin, 6.4-46.6 % by weight of waste phosphogypsum, 5.5-42.1 % by weight of magnetite, 0.58-3.9 % by weight of an organic peroxide and up to 29.9 % by weight of styrene and/or a low-molecular-weight unsaturated polyester resin.

The process according to the present invention in .ill its modifi¬ cations makes it possible to manufacture materials characterized by very good physical and chemical properties, including a very good resistance to aggresive media, also at elevated temperatures, being also perfectly suitable for processing by mechanical methods, including grinding, cut¬ ting and machining. Moreover, the materials can be reused as fillers when the goods made of them are worn out. The process according to the present invention allowing the utilization of large amounts of wastes resulted frcm the production of phosphooric acid by the wet method from phosphorite ores and consequently protecting the environment, due to the very good performance characteristics and a wide range of application of the materials according to the invention, makes it possible at the same time to save natural raw material in many cases.

SUBSTITUTE SHEET

8

The materials according to the present invention can be option¬ ally combined witch order materials such as wood, metals, glass, build¬ ing materials, either directly at the polymerization stage or after pre¬ liminary setting, using the incompletely polymerized composition. The present invention is further described by the following ex¬ amples which do not limit the range of its application.

3 3

Example I. To 2 dm of vinylester resin, 0.029 dm of 1 % sty¬ rene solution of cobalt naphthenate is added on continuous stirring and then three batches are added in turns, 3.35 dm each of waste phospho- gypsum previously roasted at 493-498 K for 2.3 hours, with a bulk

3 density of 0.9 kg/dm and particle size below 25 μm, the whole mix-

3 ture being stirred further for 15 minutes. Next, 0.13 dm of benzoyl peroxide is added and the composition is stirred for 10 minutes at most to produce 8.85 dm of a liquid material which if casted onto a founda- tion forms within 2 hours a floors with an impact strength of 1.93

2 kJ/m , a compression strength of 114 MPa and a bending strength of 37.9

MPa, suitable for use in copper electrorefining divisions.

Example II. Proceeding as in Example I, the composition prior to polymerization is rubbed in a grinder for 40-50 minutes and then 0.22

3 dm of Polimal 101 polyester resin is added, the whole is stirred for

3

10 minutes and after adding 0.135 dm of benzoyl peroxide, the resul-

3 tant polyrrerizable cctπpositiσn in a quantity of 9.05 dm is applied by means of a spray-gun onto internal surfaces of steel or concrete tanks for copper electrorefining to produce in a single spray a uniform layer with a thickness of 320 μm, consisting of 21.7 % by weight of vinyl¬ ester resin, 75 % by weight of waste phosphogxpsum, 2.2 % by weight of

Polimal 101 polyester resin and 1.1 % by weight of benzoyl peroxide.

3 3

Example III. To 2 dm of vinylester resin and 0.026 dm of 1 % sty¬ rene solution of cobalt naphthenate, being continuously stirred, two

RECTIFIED SHEET (RULE 91) ISA/EP

3 batches, 2 dm each, of previously roasted at 600 - 605 K phosphogyp¬ sum are added alternately with two batches of glass - forming oxides,

3 . . 3 3

0.55 dm each, and then on stirring 0.2 dm of styrene and 0.004 dm of dimethylaniline are added. The resultant composition in a quantity

3 3 of 5.85 dm , after adding 0.12 dm of cyclohexanone peroxide, is vised to form weights for skin-divers.

Example IV. Proceeding as in Example III, the cxamposition prior to

3 polymerization is treated with 0.003 dm of dimethylaniline for 0.7

3 hour on sjjmiltaneous rubbing, then to the whole, 0.06 dm of styrene

3 and 0.1 dm of Polimal 101 polyester resin are added. The resultant

3 3 composition with a density 1.869 kg/dm , in a quantity of 5.97 dm ,

3 after adding 0.12 dm of benzoyl peroxide, is applied, as an equiva¬ lent of baryta coating, onto the walls of a radio-isotope chamber for wet investigations, to produce in a single gun spraying a coat with a thickness of 290 μm, consisting of 23.7 % by weight of vinylester resin, 32.8 % by weight of waste phosphogypsum, 41 % by weight of glass-form¬ ing oxides, 0.6 % by weight of styrene, 0.9 % by weight of Polimal 101 polyester resin and 1 % by weight of benzoyl peroxide.

3 Example V. To 4 dm of vinylester resin on continuous stirring,

3 0.047 dm of 2 % styrene oslution of cobalt naphthenate is added an then during further stirring three batches of waste phosphogypsum,

3 roasted at 515-518 K, 1 dm each and microsphere 1.3 kg each are ad-

3 ded in turns. Finally, on continuous stirring, 0.005 dm of dimethyl-

3 aniline and 0.15 dm of Polimal 101 polyester resin are added. The re-

3 sultant composition, after adding 0.27 dm of benzoyl peroxide, is poured into moulds to produce floats to be installed in equipment used in harbours, especially for absorbing crude oil contaminations.

Example VI. Proceeding as in Example V and using phosphogypsum and

3 microsphere with a particle size of below 4 μm, 0.17 dm of Polimal 101

SUBSTITUTE SHEET

3 polyester resin and 0.28 dm of benzoyl peroxide are added to prepare a polvmerizable composition suitable for application as protective coating of ship hulls, consisting of 42.5 % by weight of vinylester re¬ sin, 22 % by weight of waste phosphogypsum, 31.8 % by weight of micro- sphere, 1.45 % by weight of Polimal 101 polyester resin and 2.2 % by weight of benzoyl peroxide.

Example VTI. Proceeding as in Example I, three batches of dry com¬ position in a quantity of 8 kg are added, consisting of even weight parts of previously roasted ai- a temperature of 487-490 K waste phos- phogypsum and magnetite with a particle size of up to 15 μm, and then on continuous stirring, 0.002 dm of benzoyl peroxide and 0.1 dm of styrene are added, completing the procedure as in Examole I. The resuL- tant polyπerizable composition, consisting og 24 % by weight of vinyl¬ ester resin, 36.9 % by weight of magnetite, 1 % by weight of styrene and 1.2 % by weight of benzoyl peroxide, is poured into moulds to pro¬ duce within 5 hours cores suitable for use in microelectronics.

SUBSTITUTE SHEET